Polymer having terminal structure including plurality of reactive silicon groups, method for manufacturing same, and use for same

ABSTRACT

A polymer (A) having, at one terminal moiety thereof, a terminal structure having two or more carbon-carbon unsaturated bonds. A reactive-silicon-group-containing polymer (B) having, at one terminal moiety thereof, a terminal structure having two or more reactive silicon groups.

TECHNICAL FIELD

The present invention relates to a novel reactive-group-containingpolymer useful, in particular, for an adhesive and others; a method formanufacturing the polymer; and a composition containing the polymer.

BACKGROUND ART

About a polymer having, in the molecule thereof, a carbon-carbonunsaturated bond, its molecular chain can be extended or a crosslinkagenetwork can be formed therein, using an ene/thiol addition reaction witha thiol compound or a hydrosilylation reaction with a hydrosilanecompound. Making use of this property, the polymer is used as a rawmaterial of adhesive compositions or curable compositions (PatentDocuments 1 and 2). When the polymer is used as the raw material ofthese curable compositions, an unsaturated bond is generally introducedinto a terminal of the molecular chain.

Such a reactive-silicon-group-containing polymer, which is obtained bycausing a hydrolyzable-group-containing hydrosilane to hydrosilylatewith a carbon-carbon unsaturated bond, is also known as amoisture-reactive polymer. The polymer is included in many industrialproducts, such as adhesives, sealing agents, coating agents, paints, andtackifiers, and is used in various fields (Patent Document 3).

As a polymer component of such a reactive-group-containing polymer,various polymers are known, examples of which include polymers eachhaving, as a main skeleton thereof, a polyoxyalkylene, saturatedhydrocarbon based polymer, or (meth)acrylate copolymer. Out of suchpolymers, a polyoxyalkylene polymer has a wide applicable scope sincethe polymer has, for example, the following characteristics: the polymeris relatively low in viscosity at room temperature to be easily handled;and a cured product obtained after reaction of this polymer also shows agood elasticity.

Physical properties of cured products and others that are obtained usinga polymer having reactive groups are affected by the structure of thepolymer, and the respective positions and the number of the reactivegroups. In particular, about the elasticity and the strength of thecured products, factors such as the crosslinkage density or thebetween-crosslinking-point molecular weight largely affect such physicalproperties. The polymer needs to have an appropriatebetween-crosslinking-point molecular weight to gain elasticity. As thepolymer is higher in crosslinkage density, the resultant cured producttends to be stronger. In order to gain a cured product having anexcellent strength, it is effective to make molecules of the polymeruniform into some degree in between-crosslinking-point molecular weight.In other words, it is preferred that respective chains of the moleculeshave, at their terminals, reactive groups. Additionally, in order tomake the molecules high in crosslinkage density, the reactive groupsneed to be efficiently present at the terminals.

Any polyoxyalkylene polymer is generally obtained through apolymerization in which an epoxy compound is subjected to ring-openingpolymerization. The polymer is obtained by, for example, apolymerization using an alkali catalyst such as KOH, a polymerizationusing a transition-metal-compound/porphyrin complex catalyst, which isobtained by causing an organic aluminum compound to react with porphyrin(Patent Document 4), a polymerization using a compositemetal-cyanide-complex catalyst (Patent Documents 5 to 12), apolymerization using a catalyst made of a polyphosphazene salt (PatentDocument 13), or a polymerization using a catalyst made of a phosphazenecompound (Patent Document 14).

A polyoxyalkylene polymer having, at its terminal, a hydroxyl group isobtained by a method as described above. By modifying the terminal groupof this hydroxyl-group-terminated polyoxyalkylene, a polyoxyalkylenepolymer having carbon-carbon unsaturated bonds can be obtained. As anexample of the modification, the following is disclosed: a method ofusing an alkali metal salt to substitute the hydroxyl group with analkoxy group, and then causing the resultant compound to react with anunsaturated-group-containing halide such as allyl chloride (PatentDocument 15); or a method of causing the hydroxyl terminal of thepolymer to react with an isocyanate compound having a carbon-carbonunsaturated bond (Patent Document 16).

Disclosed are also methods of using a composite cyanide complex as acatalyst to polymerize an epoxide monomer containing no carbon-carbonunsaturated bond, and subsequently copolymerizing the epoxide monomercontaining no carbon-carbon unsaturated bond with an epoxide monomercontaining a carbon-carbon unsaturated bond (Patent Documents 17 and18).

PRIOR ART DOCUMENTS Patent Documents

-   -   Patent Document 1: JP-B-47-3269    -   Patent Document 2: Japanese Patent No. 2866181    -   Patent Document 3: Japanese Patent No. 1801280    -   Patent Document 4: JP-A-61-215623    -   Patent Document 5: JP-B-46-27250    -   Patent Document 6: JP-B-59-15336    -   Patent Document 7: U.S. Pat. No. 3,278,457    -   Patent Document 8: U.S. Pat. No. 3,278,458    -   Patent Document 9: U.S. Pat. No. 3,278,459    -   Patent Document 10: U.S. Pat. No. 3,427,256    -   Patent Document 11: U.S. Pat. No. 3,427,334    -   Patent Document 12: U.S. Pat. No. 3,427,335    -   Patent Document 13: JP-A-10-273512    -   Patent Document 14: JP-A-11060722    -   Patent Document 15: JP-A-52-73998    -   Patent Document 16: JP-A-50-156599    -   Patent Document 17: JP-A-03-79627    -   Patent Document 18: JP-A-2001-55438

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

An object of the present invention is to introduce, more effectivelyinto a polyoxyalkylene polymer, a larger proportion of reactive groups,such as carbon-carbon unsaturated bonds or reactive silicon groups, at aterminal of the polymer, thereby providing a polymer which is a rawmaterial of a cured product having an excellent elasticity and strength;a method for manufacturing the polymer under industrially favorableconditions; and a composition including the polymer.

In the case of using a conventional method as disclosed in PatentDocument 15 or 16, a carbon-carbon unsaturated bond or carbon-carbonunsaturated bonds introducible into one hydroxyl terminal that apolyoxyalkylene polymer contains are at most one in number. In the caseof introducing reactive silyl groups further thereinto by, for example,hydrosilylation, there remains a problem that the quantity on average ofthe silyl groups introduced per terminal of the polymer is lowered inproportion.

In the case of using the method described in Patent Document 17 or 18,the polymerization for the main chain of the polymer competes with theintroduction of the reactive groups. Thus, it is difficult to controlthe molecular weight and the proportion of introduced functional groupsuniformly. As a method for introducing reactive silicon groups into aterminal (of such a polymer), known is a method of copolymerization witha reactive-silicon-group-containing epoxy compound, using a method inJP-A-2010-77432. However, this case has a problem about the removal of acatalyst for the polymerization, and a problem that the resultantpolymer is easily lowered in stability.

Means for Solving the Problems

The inventors have made eager investigations to solve the problems. As aresult, the inventors have achieved an invention described below.

Thus, the present invention relates to the following:

(1). A polymer (A) having, at one terminal moiety thereof, a terminalstructure having two or more carbon-carbon unsaturated bonds,

(2). The polymer (A) according to item (1), wherein the terminal moietyhas a structure represented by the following general formula (1):

In the formula, R¹ and R³ are each independently a bivalent bondinggroup having 1 to 6 carbon atoms and an atom of the bonding group thatis bonded to any carbon atom adjacent to the bonding group is any one ofcarbon, oxygen and nitrogen; R² and R⁴ are each independently hydrogen,or a hydrocarbon group having 1 to 10 carbon atoms; and n is an integerof 1 to 10,

(3). The polymer (A) according to item (1) or (2), wherein a hydroxylgroup or hydroxyl groups contained are 0.3 or less in number on averageper molecule of the polymer (A),

(4). The polymer (A) according to any one of items (1) to (3), having amain skeleton which is a polyoxyalkylene polymer.

(5). A method for manufacturing the polymer (A) recited in any one ofitems (1) to (4), comprising: causing an alkali metal salt to act onto apolymer having, at a terminal thereof, a hydroxyl group in an amount of0.6 equivalent or more relative to the hydroxyl group amount in thepolymer; causing the resultant to react with an epoxy compound having acarbon-carbon unsaturated bond; and further causing the resultant toreact with a halogenated hydrocarbon compound having a carbon-carbonunsaturated bond,

(6). The method for manufacturing the polymer (A) according to item (5),wherein the alkali metal salt is a sodium alkoxide, the epoxy compound,which has a carbon-carbon unsaturated bond, is allyl glycidyl ether ormethallyl glycidyl ether, and the halogenated hydrocarbon compound,which has a carbon-carbon unsaturated bond, is allyl chloride ormethallyl chloride,

(7). A reactive-silicon-group-containing polymer (B) having, at oneterminal moiety thereof, a terminal structure having two or morereactive silicon groups,

(8). A reactive-silicon-group-containing polymer (B), having reactivesilicon groups which are 1.1 or more in number on average per terminalof the polymer,

(9). A reactive-silicon-group-containing polymer (B), obtained byintroducing one or more reactive silicon groups into unsaturated bondsof the polymer (A) according to any one of items 1 to 4 byhydrosilylation reaction,

(10). A method for manufacturing a reactive-silicon-group-containingpolymer (B), comprising: introducing one or more reactive silicon groupsinto unsaturated bonds of the polymer (A) according to any one of items(1) to (4) by hydrosilylation reaction,

(11). A curing composition, comprising the polymer (A) recited in anyone of items (1) to (4),

(12). A composition, comprising the polymer (B) recited in any one ofitems (7) to (9),

(13). The curable composition according to item (12), comprising, as thepolymer (B), a reactive-silicon-group-containing polymer (B1) in which amain chain skeleton is a polyoxyalkylene polymer, and further comprisinga (meth)acrylate polymer (C) having one or more reactive silicon groups,

(14). The curable composition according to item (13), wherein thereactive silicon group(s) of the polymer (C) is/are (each) a reactivesilicon group (b3) represented by the following general formula (4):

—SiR⁵ _(3-a)Y_(a)  (4)

wherein R⁵(s) is/are (each independently) a substituted or unsubstitutedhydrocarbon group having 1 to 20 carbon atoms, Y is/are (each) ahydroxyl group or a hydrolyzable group, and a is any one of 1, 2 and 3provided that a is 3 herein.

(15). The curable composition according to item (13) or (14),comprising, as the polymer (B1), a polyoxyalkylene polymer having bothspecies of one or more reactive silicon groups (b2) which is/are (each)represented by the general formula (4) in which a is 2, and one or morereactive silicon groups (b3) which is/are (each) represented by thegeneral formula (4) in which a is 3; and/or a polyoxyalkylene polymerhaving the reactive silicon group(s) (b2) and a polyoxyalkylene polymerhaving the reactive silicon group(s) (b3),

(16). The curable composition according to item (15), wherein thereactive silicon group(s) (b2) is/are (each) a methyldimethoxysilylgroup, and the reactive silicon group(s) (b3) is/are (each) atrimethoxysilyl group,

(17). The curable composition according to any one of items (14) to(16), wherein the polymer (C) has trimethoxysilyl groups which are 1.27or more in number on average per molecule of the polymer (C),

(18). The curable composition according to item (12), further comprisinga polymer (D) having a reactive silicon group or reactive silicon groupswhich are 0.5 or more and less than 1.2 in number on average permolecule of the polymer (D),

(19). The curable composition according to item (18), wherein thepolymer (B) has a number-average molecular weight of 10000 or more andless than 35000, and the polymer (D) has a number-average molecularweight of 3000 or more and less than 10000, and

(20). The curable composition according to any one of items (12) to(19), further comprising an organopolysiloxane polymer (F) having areactive silicon group.

Effect of the Invention

The manufacturing method of the present invention makes it possible tomanufacture effectively a polymer which has, at one terminal moietythereof, a terminal structure having two or more reactive groups throughan industrially favorable process, and which is a raw material of acured product excellent in handleability and excellent in strength andelasticity. Moreover, a curable composition using the resultant polymergives a cured product excellent in mechanical strength, restorabilityand weather resistance.

MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The “terminal moiety” in the present invention includes a chain terminalof a polymeric molecular chain, and a structure in the vicinity thereof.More specifically, the wording may be defined as a group (or radical)substituted on atoms in a range extending from a terminal of a polymericmolecular chain and containing atoms the number of which is 20%,preferably 10% of the number of bonded atoms constituting the polymericmolecular chain. When represented by the number of bonded atoms, theterminal moiety may be defined as atoms in a range from a terminal atomof a polymeric molecular chain to a 30^(th) atom, more preferably a20^(th) atom, in particular preferably a 10^(th) atom from the terminalatom.

About any polymer having, at a terminal of a polymeric chain thereof, areactive group, such as a carbon-carbon unsaturated bond or reactivesilicon group, the polymeric chain can be extended or a crosslinkagenetwork can be constructed therein by making use of a reaction of thereactive group. Such a polymer makes use of this property to be changedin natures, thereby exhibiting an adhesive performance, or to form arubbery cured product. Thus, the polymer is used for many purposes. Atthis time, the presence of the reactive group at a terminal of thepolymeric chain is favorable, which has been known. In order to supplyan adhesive performance (to such a polymer) by extending the polymericchain thereof, the presence of the reactive group at the terminaleffectively attains the extension of the molecular chain. Moreover,according to the three-dimensional linkage, the polymer can ensure abetween-crosslinking-point molecular weight, also at the time ofyielding a cured product, by the presence of the reactive group at themolecular chain terminal. Thus, characteristics of the structure of thepolymeric main chain are reflected onto physical properties of the curedproduct so that the cured product can become strong. Any ordinarilyknown reactive-group-containing polymer is generally a polymer having,at each terminal moiety, a single reactive group. When such areactive-group-containing polymer is used to aim at aphysical-property-supply as described above, which makes use ofterminal-group-reaction, a defect is generated in the chain extension orthe three-dimensional crosslinkage unless the reaction efficiency is100%. As a result, expected properties may not be obtained.

Thus, the present inventors have invented a reactive-group-containingpolymer described below.

The polymer (A) of the present invention is a polymer having, at oneterminal moiety thereof, a terminal structure having two or morecarbon-carbon unsaturated bonds.

The number of terminal structures which are contained in each moleculeof the polymer (A) and which each have two or more carbon-carbonunsaturated bonds is preferably 0.5 or more, more preferably 1.0 ormore, even more preferably 1.1 or more, most preferably 1.5 or more onaverage. The upper limit thereof is preferably 4 or less, morepreferably 3 or less. It is preferred that the polymer (A) hardly has,at any moiety other than its terminal moieties, carbon-carbonunsaturated bonds. Even when the polymer (A) has one or morecarbon-carbon unsaturated bonds thereat, the number thereof ispreferably 2 or less. In particular preferably, the polymer (A) does notsubstantially have any carbon-carbon unsaturated bond thereat.

As far as the polymer (A) has, at one terminal moiety thereof, two ormore carbon-carbon unsaturated bonds, the polymer (A) may have, at adifferent terminal moiety thereof, a terminal structure having less than2 carbon-carbon unsaturated bonds.

The terminal structure of the polymer (A) having two or morecarbon-carbon unsaturated bonds is represented by the following generalformula (1):

In the formula, R¹ and R³ are each independently a bivalent bondinggroup having 1 to 6 carbon atoms and an atom of the bonding group thatis bonded to any carbon atom adjacent to the bonding group is any one ofcarbon, oxygen and nitrogen; R² and R⁴ are each independently hydrogen,or a hydrocarbon group having 1 to 10 carbon atoms; and n is an integerof 1 to 10, preferably 1 or 2. A specific example of the carbon-carbonunsaturated bond is preferably an allyl group structure or a methallylgroup structure since the introduction of the structure is easy.However, the carbon-carbon unsaturated bond is not limited thereto.

Examples of R¹ include CH₂OCH₂, CH₂O, CH₂ and the like.

Examples of R² include a hydrogen atom, methyl and ethyl groups and thelike.

Examples of R³ include CH₂, CH₂CH₂ and the like.

Examples of R⁴ include a hydrogen atom, methyl and ethyl groups and thelike.

The polymer (A) has carbon-carbon unsaturated bonds which are preferablyfrom 1.1 to 5 both inclusive in number, more preferably from 1.2 to 3both inclusive in number, even more preferably from 1.5 to 2.5 bothinclusive in number, in particular preferably from 1.7 to 2.5 bothinclusive in number on average per terminal moiety of the polymer (A).

The number-average molecular weight of the polymer (A) is preferablyfrom about 3,000 to 100,000, more preferably from 3,000 to 50,000, inparticular preferably from 3,000 to 30,000 in terms of that ofpolystyrene through GPC. If the number-average molecular weight is lessthan 3,000, the proportion of introduced reactive silicon groups resultsin being large so that an inconvenience may be caused for productioncosts. If the number-average molecular weight is more than 100,000, thepolymer (A) is high in viscosity to tend to be deteriorated inworkability.

The molecular weight distribution (Mw/Mn) of the polymer (A) is notparticularly limited. The distribution is preferably narrow to be lessthan 2.0, and is more preferably 1.6 or less, even more preferably 1.5or less, in particular preferably 1.4 or less, or 1.2 or less.

The main chain structure of the polymer (A) may be linear, or may have abranched chain. Since the polymer (A) of the present invention ischaracterized in that reactive groups are caused to be localized at itsterminal(s), the main chain structure is preferably linear.

The skeleton of the main chain of the polymer (A) is not particularlylimited, and may be a main chain skeleton that may be of various types.Examples thereof include polyoxyalkylene polymers such aspolyoxyethylene, polyoxypropylene, polyoxybutylene,polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, andpolyoxypropylene-polyoxybutylene copolymer; hydrocarbon polymers such asethylene-propylene copolymer, polyisobutylene, a copolymer made fromisobutylene, and isoprene or some other, polychloroprene, polyisoprene,a copolymer made from isoprene or butadiene, acrylonitrile and/orstyrene or some other, polybutadiene, and a copolymer made from isopreneor butadiene, acrylonitrile, and styrene or some other, and hydrogenatedpolyolefin polymers each obtained by hydrogenating any one of thesepolyolefin polymers; polyester polymers each obtained by condensing adibasic acid such as adipic acid, and glycol, or causing a lactone toundergo ring-opening polymerization; (meth)acrylate polymers eachobtained by radical-polymerizing a monomer such as ethyl (meth)acrylateor butyl (meth)acrylate; vinyl polymers each obtained byradical-polymerizing a monomer such as a (meth)acrylate monomer, vinylacetate, acrylonitrile, or styrene; graft polymers each obtained bypolymerizing a vinyl monomer in any one of these polymers; polysulfidepolymers; polyamide polymers such as polyamide 6 obtainable by thering-opening polymerization of ε-caprolactam, polyamide 6,6 obtainableby the polycondensation of hexamethylenediamine and adipic acid,polyamide 6,10 obtainable by the polycondensation ofhexamethylenediamine and sebacic acid, polyamide 11 obtainable by thepolycondensation of ε-aminoundecanoic acid, polyamide 12 obtainable bythe ring-opening polymerization of ε-aminolaurolactam, and copolymerizedpolyamides each having two or more components of these polyamides; andorganic polymers such as polycarbonate polymer produced bypoly-condensing bisphenol A and carbonyl chloride, and dially phthalatepolymers. These polymers may each be in a mixed form of two or more of ablock form, a graft form and other forms. Of these examples, preferredare saturated hydrocarbon polymers such as polyisobutylene, hydrogenatedpolyisoprene and hydrogenated polybutadiene, polyoxyalkylene polymers,and (meth)acrylate polymers since these polymers are relatively low inglass transition temperature and respective cured products obtained fromthe polymers are excellent in cold resistance.

The polymer (A) may have any one of the above-mentioned various mainchain skeletons, or may be a mixture of polymers having different onesof the main chain skeletons. The mixture may be a mixture obtained byproducing its polymers separately from each other and then mixing thepolymers with each other, or a mixture obtained by producing itscomponents simultaneously into any mixture composition.

The glass transition temperature of the polymer (A) is not particularlylimited. The glass transition temperature is preferably 20° C. or lower,more preferably 0° C. or lower, in particular preferably −20° C. orlower. If the glass transition temperature is higher than 20° C., thepolymer (A) may become high in viscosity in winter or in cold districtsto be difficult to handle. Moreover, the resultant cured product may belowered in flexibility to be declined in elongation. The glasstransition temperature can be obtained by DSC measurement in accordancewith a measuring method prescribed in JIS K 7121.

The saturated hydrocarbon polymers, the polyoxyalkylene polymers, the(meth)acrylate polymers and other organic polymers are preferred sincewhen the polymers are each used as a base polymer for an adhesive orsealing material, there is rarely caused a pollution based on, forexample, the shift of low molecular weight components therein onto anadherend.

The polyoxyalkylene polymers and the (meth)acrylate polymers arepreferred since the polymers are high in moisture permeability andadhesiveness, and are excellent in depth curability when made into aone-pack type composition. The polyoxyalkylene polymers are particularlypreferred.

The polyoxyalkylene polymers are each a polymer having repeating unitseach represented by —R⁷—O— wherein R⁷ is a linear or branched alkylenegroup having 1 to 14 carbon atoms. R⁷ is more preferably a linear orbranched alkylene group having 2 to 4 carbon atoms. Specific examples ofthe repeating unit represented by —R⁵—O— include —CH₂O—, —CH₂CH₂O—,—CH₂CH(CH₃)O—, —CH₂CH(C₂H₅)O—, —CH₂C(CH₃) (CH₃)O—, and —CH₂CH₂CH₂CH₂O—.The main chain structure of each of the polyoxyalkylene polymers may bemade of only one repeating unit species, or two or more repeating unitspecies. When the polymer (A) is used, in particular, as a sealant, anadhesive or the like, the polyoxyalkylene polymer is preferably apolymer comprising a polyoxypropylene polymer in which the proportion ofrepeating units of oxypropylene is 50% or more by weight, preferably 80%or more by weight of the main chain structure of the polymer since thepolymer is amorphous and is relatively low in viscosity.

The polyoxyalkylene polymer is preferably a polymer obtained by thering-opening polymerization reaction of a cyclic ether compound in thepresence of an initiator, using a polymerization catalyst.

Examples of the cyclic ether compound include ethylene oxide, propyleneoxide, butylene oxide, tetramethylene oxide, and tetrahydrofuran. Thesecyclic ether compounds may be used alone or in any combination of two ormore thereof. It is preferred to use, out of these cyclic ethercompounds, in particular, propylene oxide since a polyether polymeramorphous and relatively low in viscosity can be obtained therefrom.

Specific examples of the initiator include alcohols such as ethyleneglycol, propylene glycol, butanediol, hexamethylene glycol, neopentylglycol, diethylene glycol, dipropylene glycol, triethylene glycol,glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, andsorbitol; and polyoxyalkylene polymers each having a number-averagemolecular weight of 300 to 4,000, such as polyoxypropylene diol,polyoxypropylene triol, polyoxyethylene diol, and polyoxyethylene triol.

The polymerization method for the polyoxyalkylene polymer is notparticularly limited, and may be, for example, a polymerization using analkali catalyst such as KOH, a polymerization disclosed inJP-A-61-215623, using a transition-metal-compound/porphyrin complexcatalyst, which is obtained by causing an organic aluminum compound toreact with porphyrin, a polymerization disclosed in each ofJP-B-46-27250, JP-B-59-15336, U.S. Pat. No. 3,278,457, U.S. Pat. No.3,278,458, U.S. Pat. No. 3,278,459, U.S. Pat. No. 3,427,256, U.S. Pat.No. 3,427,334, U.S. Pat. No. 3,427,335, and other publications, using acomposite metal-cyanide-complex catalyst, a polymerization disclosed inJP-A-10-273512, using a catalyst made of a polyphosphazene salt, or apolymerization disclosed in JP-A-11060722, using a catalyst made of aphosphazene compound.

The above-mentioned saturated hydrocarbon polymers are each a polymerwhich does not substantially have any carbon-carbon unsaturated bondother than such bonds in an aromatic ring. A polymer constituting itsskeleton can be obtained by, for example, a method (1) of polymerizingan olefin compound having 2 to 6 carbon atoms, such as ethylene,propylene, 1-butene or isobutylene, as a main monomer, or a method (2)of homo-polymerizing a diene compound such as butadiene or isoprene, orcopolymerizing the diene compound with the olefin compound, and thenhydrogenating the resultant copolymer. Of these saturated hydrocarbonpolymers, any isobutylene polymer or hydrogenated polybutadiene polymeris preferred since a functional group is easily introduced into itsterminal(s), the molecular weight thereof is easily controllable, andfurther the number of its terminated functional groups can be increased.The isobutylene polymer is more preferred.

A polymer having a main chain skeleton that is a saturated hydrocarbonpolymer has features of being excellent in heat resistance, weatherresistance, endurance and moisture blocking performance.

The isobutylene polymer may be a polymer in which all repeating unitsare each an isobutylene unit, or a copolymer composed of isobutyleneunits and other repeating units (each made of a monomer). From theviewpoint of rubber properties, the isobutylene polymer is preferably aisobutylene polymer having 50% or more by weight of repeating units eachoriginating from isobutylene, more preferably one having 80% or more byweight of the units, in particular preferably one having 90 to 99% byweight of the units.

The method for synthesizing the unsaturated hydrocarbon polymer is notparticularly limited, and may be various polymerization methods thathave been hitherto reported. The method is preferably livingpolymerization about which many reports have been made, particularly, inrecent years. Using, out of examples of the living polymerization,iniferter polymerization (J. P. Kennedy et al., J. Polymer Sci., PolymerChem. Ed. 1977, vol. 15, p. 2869) discovered by Kennedy et al., thesaturated hydrocarbon polymer, in particular, isobutylene polymer caneasily be produced. It is known that a polymer having a molecular weightof about 500 to 10,000 can be obtained with a molecular weightdistribution of 1.5 or less by the polymerization, and variousfunctional groups can be introduced into one or more molecular terminalsthereof.

The (meth)acrylate monomer constituting each of the above-mentioned(meth)acrylate (co)polymers is not particularly limited. The monomer maybe various monomers. Specific examples thereof include methyl(meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl(meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate,tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl(meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate,n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl(meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl(meth)acrylate, tolyl (meth)acrylate, benzyl (meth)acrylate,2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate,2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl(meth)acrylate, glycidyl (meth)acrylate, (3-trimethoxysilyl)propyl(meth)acrylate, (3-dimethoxymethylsilyl)propyl (meth)acrylate,(2-trimethoxysilyl)ethyl (meth)acrylate, (2-dimethoxymethylsilyl)ethyl(meth)acrylate, trimethoxysilylmethyl (meth)acrylate,(dimethoxymethylsilyl)methyl (meth)acrylate, an ethylene oxide adduct of(meth)acrylic acid, trifluoromethylmethyl (meth)acrylate,2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl(meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate,perfluoroethyl (meth)acrylate, trifluoromethyl (meth)acrylate,bis(trifluoromethyl)methyl (meth)acrylate,2-trifluoromethyl-2-perfluoroethylethyl (meth)acrylate,2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl(meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, and other(meth)acrylic acid based monomers.

Examples of the monomer unit other than the above-mentioned monomersinclude acrylic acids such as acrylic acid and methacrylic acid; andmonomers each containing an amide group, such as N-methylolacrylamide,and N-methylolmethacrylamide, monomers each containing an epoxy group,such as glycidyl acrylate, and glycidyl methacrylate, and monomers eachcontaining a nitrogen-containing group, such as diethylaminoethylacrylate, and diethylaminoethyl methacrylate.

The above-mentioned (meth)acrylate polymers may each a polymer obtainedby copolymerizing a (meth)acrylate monomer with a vinyl monomercopolymerizable with this monomer. The vinyl monomer is not particularlylimited. Examples thereof include styrene monomers, such as styrene,vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, andsalts thereof; fluorine-containing vinyl monomers such asperfluoroethylene, perfluoropropylene, and vinylidene fluoride;silicon-containing vinyl monomers such as vinyltrimethoxysilane andvinyltriethoxysilane; maleic anhydride, maleic acid, and monoalkylesters and dialkyl esters of maleic acid; fumaric acid, and monoalkylesters and dialkyl esters of fumaric acid; maleimide monomers such asmaleimide, methylmaleimide, ethylmaleimide, propylmaleimide,butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide,stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide;nitrile-group-containing monomers such as acrylonitrile andmethacrylonitrile; amide-group-containing monomers such as acrylamideand methacrylamide; vinyl ester monomers such as vinyl acetate, vinylpropionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenylmonomers such as ethylene and propylene; conjugated diene monomers suchas butadiene and isoprene; and vinyl chloride, vinylidene chloride, allychloride, and allyl alcohol. Two or more of these monomers are alsousable as copolymerizable components.

Out of (meth)acrylate polymers obtained from these monomers, copolymerseach made from a styrene monomer and a (meth)acrylic acid monomer arepreferred since the copolymers are excellent in physical properties.More preferred are (meth)acrylate polymers each made from an acrylatemonomer and a methacrylate monomer. Particularly preferred are acrylatepolymers each made from an acrylate monomer.

When the polymer (A) is used, in particular, for ordinary architectureor the like, a butyl acrylate polymer made from a butyl acrylate monomeris preferred from a viewpoint that a composition therefor is required tohave a low viscosity and a cured product therefor is required to have alow modulus, and a high elongation, weather resistance and heatresistance, and other physical properties. When the polymer (A) is usedfor automobiles or other articles for which oil resistance and othersare required, a copolymer made mainly of ethyl acrylate is preferred. Apolymer made from ethyl acrylate is excellent in oil resistance, but maybe somewhat poor in low-temperature property (cold resistance). Thus, inorder to improve the polymer in low-temperature property, units of ethylacrylate may be partially substituted with units of butyl acrylate.However, as the proportion of butyl acrylate is made larger, the goodoil resistance is further damaged. For articles for which oil resistanceis required, the proportion is preferably 40% or less, more preferably30% or less. In order to improve the low-temperature property and otherswithout damaging the oil resistance, it is also preferred to use acompound in which oxygen is introduced into an alkyl group as a sidechain, such as 2-methoxyethyl acrylate or 2-ethoxyethyl acrylate.

However, the introduction of an alkoxy group, which has an ether bond,into the side chain tends to make the heat resistance poor. Thus, it ispreferred that the proportion thereof is 40% or less when the polymer isrequired to have heat resistance. The proportion may be varied to gainan appropriate polymer, considering required oil resistance, heatresistance, low-temperature property, and other physical properties inaccordance with the usage (of the final product) that may be of varioustypes, and required purposes. An example in which a balance between oilresistance, heat resistance, low-temperature property and other physicalproperties is excellent is a copolymer composed of ethyl acrylate, butylacrylate and 2-methoxyethyl acrylate (ratio by weight:40-50/20-30/30-20) although the example is not limited to thiscopolymer. In the present invention, these preferred monomers may becopolymerized or block-copolymerized with a different monomer. At thistime, it is preferred that these preferred monomers are contained in aproportion of 40% or more by weight.

The main chain skeleton of the polymer (A) may contain a differentcomponent, such as a urethane bond component, as far as the advantageouseffects of the present invention are not largely damaged. The urethanebond component is not particularly limited, and may be a group producedby a reaction between an isocyanate group and an active-hydrogen group(hereinafter referred to also as an amide segment group hereinafter).

A cured product obtained by curing a curable composition containing, inits main chain, a urethane bond or ester bond may gain, through theeffect of hydrogen bond or some other effect, advantages that theproduct gains a high hardness and is improved in strength, and otheradvantages. However, the urethane bond may be cleaved by heat or someother. In order to give such properties to the curable composition ofthe present invention, an amide segment group may be introduced into thepolymer (A), or any amide segment group dares to be excluded from thepolymer (A). The polymer (A) having an amide segment group tends to behigh in viscosity. Moreover, the polymer (A) having an amide segmentgroup may be improved in curability.

Specific examples of the amide segment group include a urethane group,which is produced by a reaction between an isocyanate group and ahydroxyl group, or a reaction between an amino group and carbonate; aurea group, which is produced by a reaction between an isocyanate groupand an amino group; and a thiourethane group, which is produced by areaction between an isocyanate group and a mercapto group. In thepresent invention, examples of the amide segment group also includegroups each produced by a further reaction between active hydrogen inany one of the urethane, urea and thiourethane groups, and an isocyanategroup.

In the polymer (A) used in the present invention, polymers havingdifferent main chain skeletons are usable in a mixture form.

In the case of mixing, for example, a polyoxyalkylene polymer with a(meth)acrylate polymer, one or more alkyl (meth)acrylate monomers arecontained in a proportion of 50% or more by weight, more preferably in aproportion of 70% or more by weight from the viewpoint of compatibilitytherebetween. It is preferred to use, as the alkyl (meth)acrylatemonomer(s), an alkyl (meth)acrylate monomer having an alkyl group having1 to 8 carbon atoms (p1), and an alkyl (meth)acrylate monomer having analkyl group having 10 to 30 carbon atoms (p2). In this case, the ratioby weight of the alkyl (meth)acrylate monomer (p1) to the alkyl(meth)acrylate monomer (p2) (p1/p2) is preferably from 95/5 to 40/60,more preferably from 90/10 to 60/40.

An example of a combination in which no component (p2) is used ispreferably a combination of methyl (meth)acrylate, and butyl(meth)acrylate with an alkyl (meth)acrylate monomer having an alkylgroup having 7 to 9 carbon atoms, or a combination of an alkyl(meth)acrylate monomer having an alkyl group having 1 or 2 carbon atomswith an alkyl (meth)acrylate monomer having an alkyl group having 7 to 9carbon atoms from the viewpoint of the compatibility thereof withpolyether polymer.

The method for synthesizing the (meth)acrylate polymer is notparticularly limited, and may be any known method. However, a polymerobtained by an ordinary free-radical polymerization, in which an azocompound, a peroxide or the like is used as a polymerization initiator,generally has problems of having a large molecular weight distributionvalue of 2 or more and being large in viscosity. It is thereforepreferred to use living radical polymerization in order to yield a(meth)acrylate polymer having a narrow molecular weight distribution anda low viscosity and having, at a molecular chain terminal thereof,crosslinkable functional groups in a high proportion.

A specific example of the free radical polymerization is solutionpolymerization or bulk polymerization in which a polymerizationinitiator, a chain transfer agent, a solvent and others are added (to amonomer) and the monomer is polymerized at 50 to 150° C.

Examples of the polymerization initiator include azo compounds such as2,2′-azobis(2-methylbutyronitrile), dimethyl2,2′-azobis(2-methylpropionate), 2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),2,2′-azobis[N-(2-propenyl)-2-methylpropionamide], and1,1′-azobis(cyclohexane-1-carbonitrile); diacyl peroxides such asbenzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoylperoxide, lauroyl peroxide, p-chlorobenzoyl peroxide, anddi(3,5,5-trimethylhexanoyl) peroxide; peroxy dicarbonates such asdiisopropyl perdicarbonate, di-sec-butyl perdicarbonate, di-2-ethylhexylperdicarbonate, di-1-methylheptyl perdicarbonate, di-3-methoxybutylperdicarbonate, and dicyclohexyl perdicarbonate; peroxy esters such astert-butyl perbenzoate, tert-butyl peracetate, tert-butylper-2-ethylhexanoate, tert-butyl perisobutyrate, tert-butyl perpivalate,tert-butyl diperadipate, and cumyl perneodecanoate; ketone peroxidessuch as methyl ethyl ketone peroxide, and cyclohexanone peroxide;dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide,tert-butylcumyl peroxide, and1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane; hydroperoxides suchas cumene hydroxyperoxide and tert-butylhydroperoxide;1,1-di(tert-hexylperoxy)-3,3,5-trimethylcylochexane, and otherperoxides. These polymerization initiators may be used alone or in anycombination of two or more thereof.

Examples of the chain transfer agent include mercapto-group-containingcompounds such as n-dodecylmercaptane, tert-dodecylmercaptane, andlaurylmercaptane. In the case of desiring to introduce reactive silicongroups to a molecular chain terminal of the (meth)acrylate polymer, itis preferred to use a mercaptosilane compound, which has a reactivesilicon group and a mercapto group, such as3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane,3-mercaptopropylchloromethyldimethoxysilane,3-mercaptopropylmethoxymethyldimethoxysilane,marcaptomethyltrimethoxysilane, or(mercaptomethyl)dimethoxymethylsilane. These may be used alone or in anycombination of two or more thereof.

Examples of the solvent include aromatic compounds such as toluene,xylene, styrene, ethylbenzene, p-dichlorobenzene, di-2-ethylhexylphthalate, and di-n-butyl phthalate; hydrocarbon compounds such ashexane, heptane, octane, cyclohexane, and methylcyclohexane; carboxylicacid ester compounds such as butyl acetate, n-propyl acetate, andisopropyl acetate; ketone compounds such as methyl isobutyl ketone andmethyl ethyl ketone; dialkyl carbonate compounds such as dimethylcarbonate and diethyl carbonate; and alcohol compounds such as1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol,tert-butyl alcohol, and amyl alcohol. Of these compounds, one or moreselected from dialkyl carbonate compounds and alcohol compounds arepreferred from the viewpoint of a matter that the compounds are not anyguideline value established substance according to the Ministry ofHealth, Labor and Welfare in Japan, odor, a load onto the environment,and others. More preferred are dimethyl carbonate, 1-propanol,2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, and tert-butylalcohol, and particularly preferred are 2-propanol and isobutyl alcoholfrom the viewpoint of the boiling point thereof, and a matter that theemission of all volatile organic compounds from the composition(concerned) can be restrained, the emission being measured according toa measuring method described in GEV Specification and ClassificationCriteria, Feb. 14, 2001 version, prescribed by GEV (GemeinschaftEmissionskontrollierte Verlegewerkstoffe, e.V.).

The monomer may be polymerized together with a polyether polymer, aplasticizer that will be detailed later, or some other besides thesolvent.

Living radical polymerization is a polymerization method making itpossible to yield a polymer having any molecular weight, a narrowmolecular weight distribution, and a low viscosity, and furtherintroduce a monomer having a specific functional group into asubstantially arbitrary position of the polymer, which is different fromthe situation according to the free-radical polymerization. Livingpolymerization denotes, in a narrow sense, a polymerization in which aterminal (of a molecular chain) constantly has activity so that thegrowth of the molecular chain continues. In general, the term “livingpolymerization” also includes pseudo-living polymerization, in whichterminals are growing in the state that inactivated ones and activatedones, out of the terminals, are in an equilibrium state.

Examples of the living radical polymerization include a polymerizationusing a cobalt porphyrin complex, as described in Journal of theAmerican Chemical Society (J. Am. Chem. Soc.), 1994, vol. 16, p. 7943; apolymerization using nitrooxide radicals, as described inJP-A-2003-500378; and atom transfer radical polymerization (ATRPmethod), using, for example, an organic halide or a halogenated sulfonylcompound as an initiator, and using a transition metal complex as acatalyst, as described in JP-A-11-130931. In the present invention, theatom transfer radical polymerization also includes, as an example, theso-called reverse atom transfer radical polymerization as described inMacromolecules, 1999, vol. 32, p. 2872, i.e., a polymerization ofcausing an ordinary radical initiator such as a peroxide to act onto ahighly-oxidized-state species obtained when an ordinary atom transferradical polymerization catalyst generates radicals, for example, Cu(II′) obtained when copper (II) is used as a catalyst, so as to producean equilibrium state similar to that produced by atom transfer radicalpolymerization.

Out of examples of the living radical polymerization, the “atom transferradical polymerization” of polymerizing a (meth)acrylate monomer, usingan organic halide or a halogenated sulfonyl compound as an initiator,and using a transition metal composition as a catalyst is more preferredas a method for producing a (meth)acrylate polymer having a specificfunctional group for the following reasons: this polymerization hascharacteristics of the above-mentioned “living radical polymerization”;and further the living polymer has, at a terminal thereof, a halogen orany other species that is relatively favorable for functional groupconverting reaction, and thus a large flexibility is allowable fordesigning the initiator or catalyst. This atom transfer radicalpolymerization is described in, for example, Matyjaszewski et al.,Journal of the American Chemical Society (J. Am. Chem. Soc.), 1995, vol.117, p. 5614.

It is allowable to use, as a polymerization method other than thesemethods, for example, a method of using a metallocene catalyst, and athiol compound having, in the molecule thereof, at least one reactivesilicon group to yield a (meth)acrylate polymer, as disclosed inJP-A-2001-040037, or a high-temperature continuous polymerization ofusing an agitating-vessel-type reactor to polymerize a vinyl monomercontinuously, as disclosed in JP-A-57-502171, JP-A-59-006207, orJP-A-60-511992.

The polymer may contain, as the main chain skeleton thereof, a urethanebond component or any other component as far as the advantageous effectsof the present invention are not largely damaged.

The urethane bond component is not particularly limited, and may be agroup produced by a reaction between an isocyanate group and anactive-hydrogen group (hereinafter referred to also as an amide segmentgroup). The amide segment group is a group represented by —NR⁶(C═O)wherein R⁶ represents a hydrogen atom, or a substituted or unsubstitutedorganic group having 1 to 20 carbon atoms. The amide segment group isnot particularly limited. Examples thereof include a urethane group,which is produced by a reaction between an isocyanate group and ahydroxyl group; a urea group, which is produced by a reaction between anisocyanate group and an amino group; a thiourethane group, which isproduced by a reaction between an isocyanate group and a mercapto group,and any other functional group having an amide bond; and groups eachproduced by a further reaction between active hydrogen in any one of theurethane, urea and thiourethane groups, and an isocyanate group.

About a cured product obtained by curing a curable composition made ofthe polymer containing, in the main chain thereof, a urethane bond orester bond, the main chain may be unfavorably cleaved at its urethanebond or ester bond moiety by heat or some other, so that the curedproduct may be remarkably lowered in strength.

When the proportion of the quantity of the amide segment group is largein the main chain skeleton of the polymer (A) of the present invention,the polymer tends to be increased in viscosity. Moreover, the viscositymay rise after the polymer (A) is stored. Thus, the resultantcomposition may be lowered in workability. Furthermore, as describedabove, the amide segment group may be cleaved by heat or some other. Itis therefore preferred that the polymer (A) does not substantiallycontain any amide segment group in order to obtain a compositionexcellent in storage stability and workability. Contrarily, by the amidesegment group in the main chain skeleton of the polymer (A), the curablecomposition tends to be improved in curability. Accordingly, when themain chain skeleton of the polymer (A) contains the amide segment group,the number of amide segments (of this group) is preferably from 1 to 10,more preferably from 1.5 to 5, in particular preferably from 2 to 3 onaverage per molecule of the polymer (A). If the number is less than 1,the curable composition may be insufficient in curability. If the numberis more than 10, the polymer may be raised in viscosity to be difficultto handle.

Specific examples of the amide segment group include a urethane group,which is produced by a reaction between an isocyanate group and ahydroxyl group, or a reaction between an amino group and carbonate; aurea group, which is produced by a reaction between an isocyanate groupand an amino group; and a thiourethane group, which is produced by areaction between an isocyanate group and a mercapto group. In thepresent invention, examples of the amide segment group of theabove-mentioned general formula also include groups each produced by afurther reaction between active hydrogen in any one of the urethane,urea and thiourethane groups, and an isocyanate group.

A description is herein made about a method for introducing reactivegroups into the polymer (A). In the present invention, the method forintroducing, into the polymer, two or more carbon-carbon unsaturatedbonds per terminal of the polymer may be a method of causing an alkalimetal salt to act onto a hydroxyl-group-terminated polymer, andsubsequently causing an epoxy compound having a carbon-carbonunsaturated bond firstly to react with the resultant and causing ahalogenated hydrocarbon compound having a carbon-carbon unsaturated bondsecondly to react with the resultant. The use of this method makes itpossible to attain the introduction of the reactive groups effectivelyand stably while the molecular weight and the molecular weightdistribution of the main chain of the polymer are controlled inaccordance with polymerization conditions.

In the present invention, the alkali metal salt is used when the epoxycompound having a carbon-carbon unsaturated bond is caused to react withthe hydroxyl-group-terminated polymer; the use of the alkali metal saltmakes it possible to cause the epoxy compound having a carbon-carbonunsaturated bond to react with terminal moieties of all molecules of thepolymer uniformly. In the case of using not the alkali metal salt but azinc hexacyanocobaltate complex, the epoxy compound having acarbon-carbon unsaturated bond unfavorably reacts selectively withmolecules of the polymer that are low in molecular weight, so thatcarbon-carbon unsaturated bonds (of molecules of the epoxy compound) arelocally introduced into terminal moieties of parts of the polymermolecules. Thus, this case is unfavorable.

Examples of the alkali metal salt used in the present invention includesodium hydroxide, sodium alkoxides, potassium hydroxide, potassiumalkoxides, lithium hydroxide, lithium alkoxides, cesium hydroxide, andcesium alkoxides. The salt is preferably sodium hydroxide, sodiummethoxide, sodium ethoxide, potassium hydroxide, potassium methoxide, orpotassium ethoxide, and is more preferably sodium methoxide or potassiummethoxide from the viewpoint of the easiness of the handling thereof,and solubility. Sodium methoxide is particularly preferred from theviewpoint of availability. The alkali metal salt may be used in thestate of being dissolved in a solvent.

About the addition amount of the alkali metal salt used in the presentinvention, the lower limit of the ratio by mole of the salt to thehydroxyl groups of the polymer is preferably 0.5 or more, morepreferably 0.6 or more, even more preferably 0.7 or more, or 0.8 ormore. The upper limit thereof is preferably 1.2 or less, more preferably1.0 or less. If the addition amount of the alkali metal salt isexcessively small, the reaction does not advance sufficiently. If theaddition amount is excessively large, the alkali metal salt remains asan impurity so that a side reaction may unfavorably advance.

The alkali metal salt is used to alkoxylate hydroxyl groups in thepolyoxyalkylene polymer. In order to advance this reaction efficiently,it is preferred to remove water and any alcohol other than thehydroxyl-group-containing polymer from the reaction system. For theremoval, it is advisable to use a known method, such as heatingevaporation, devolatilization under reduced pressure, spraygasification, thin-membrane evaporation, or azeotropic devolatilization.

The temperature when the alkali metal salt is caused to act ispreferably from 50 to 150° C. both inclusive, more preferably from 110to 140° C. both inclusive. The period when the alkali metal salt iscaused to act is preferably from 10 minutes to 5 hours both inclusive,more preferably from 30 minutes to 3 hours both inclusive.

The epoxy compound used in the present invention, which has acarbon-carbon unsaturated bond, is in particular preferably a compoundby the following general formula (2):

In the formula, R¹ and R² are the same as described above. Specifically,the epoxy compound is preferably allyl glycidyl ether, methallylglycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadienemonooxide, or 1,4-cyclopentadiene monoepoxide from the viewpoint ofreactive activity, and is in particular preferably ally glycidyl ether.

The addition amount of the epoxy compound used in the present invention,which has a carbon-carbon unsaturated bond, may be any amount,considering the amount and the reactivity of carbon-carbon unsaturatedbonds introduced into the polymer. In particular, the lower limit of theratio by mole of the epoxy compound to the hydroxyl groups contained inthe polymer is preferably 0.2 or more, more preferably 0.5 or more. Theupper limit thereof is preferably 5.0 or less, more preferably 2.0 orless.

In the present invention, the reaction temperature when the epoxycompound, which has a carbon-carbon unsaturated bond, is caused toundergo a ring-opening addition reaction with thehydroxyl-group-containing polymer is preferably from 60 to 150° C. bothinclusive, more preferably from 110 to 140° C. both inclusive. As thetemperature is lower, the reaction less advances. If the temperature isexcessively high, the main chain of the polyoxyalkylene polymer may beunfavorably decomposed. The reaction time is preferably from 10 minutesto 5 hours both inclusive, more preferably from 30 minutes to 3 hoursboth inclusive.

The halogenated hydrocarbon compound used in the present invention,which has a carbon-carbon unsaturated bond, is in particular preferablya compound represented by the following general formula (3):

In the formula, R³ and R⁴ are the same as described above, and X is ahalogen atom. Specific examples thereof include vinyl chloride, allylchloride, methallyl chloride, vinyl bromide, ally bromide, methallylbromide, vinyl iodide, ally iodide, and methallyl iodide. Ally chlorideand methallyl chloride are more preferred from the viewpoint of theeasiness of the handling thereof.

The addition amount of the halogenated hydrocarbon compound, which has acarbon-carbon unsaturated bond, is not particularly limited. The lowerlimit of the ratio by mole of the compound to hydroxyl groups containedin the polyoxyalkylene polymer is preferably 0.7 or more, morepreferably 1.0 or more. The upper limit thereof is preferably 5.0 orless, more preferably 2.0 or less.

The temperature when the halogenated hydrocarbon compound, which has acarbon-carbon unsaturated bond, is caused to react is preferably from 50to 150° C. both inclusive, more preferably from 110 to 140° C. bothinclusive. The reaction time is preferably from 10 minutes to 5 hoursboth inclusive, more preferably from 30 minutes to 3 hours bothinclusive.

The number of hydroxyl groups contained in each molecule of the polymer(A) obtained after the above-mentioned reaction is preferably 0.3 orless, more preferably 0.1 or less in order that the polymer (A) may keepa sufficient stability even when stored over a long term.

The carbon-carbon unsaturated bonds of the polymer (A) of the presentinvention are usable at will. The bonds are usable for, for example, abase polymer of an addition-curing-type curable composition making useof hydrosilylation reaction with a polyhydrosilyl compound, ene-thiolreaction with a polythiol compound. The polymer (A) is also usable as amacromonomer. Furthermore, using the above-mentioned reaction, aterminal of the polymer (A) can be modified.

The polymer (B) of the present invention is a polymer having, at oneterminal moiety thereof, two or more reactive silicon groups. The use ofthe polymer (B) may improve bonding (performance). It has been verifiedthat a curable composition good in adhesiveness, in particular, underwet-heat resistant conditions is obtained. Water-resistant bonding, oran improvement in adhesiveness onto concrete can be also expected.

The number of a terminal structure or terminal structures which arecontained in each molecule of the polymer (B) and have two or morereactive silicon groups is 0.5 or more, more preferably 1.0 or more,even more preferably 1.1 or more, most preferably 1.5 or more onaverage. The upper limit thereof is preferably 4 or less, morepreferably 3 or less.

It is preferred that the polymer (B) hardly has, at any moiety otherthan its terminal moieties, reactive silicon groups. Even when thepolymer (B) has one or more reactive silicon groups thereat, the numberthereof is preferably 2 or less. In particular preferably, the polymer(B) does not substantially have any reactive silicon group thereat.

As far as the polymer (B) has, at one terminal moiety thereof, two ormore reactive silicon groups, the polymer (B) may have, at a differentterminal moiety thereof, a terminal structure having less than 2reactive silicon groups.

The polymer (B) has reactive silicon groups which are preferably from1.1 to 5 both inclusive in number, more preferably from 1.2 to 3 bothinclusive in number, even more preferably from 1.5 to 2.5 both inclusivein number on average per terminal of the polymer (B).

The reactive silicon groups of the polymer (B) are each represented bythe following general formula (4):

—SiR⁵ _(3-a)Y_(a)  (4)

wherein R⁵(s) is/are (each independently) a substituted or unsubstitutedhydrocarbon group having 1 to 20 carbon atoms, Y is a hydroxyl group ora hydrolyzable group, and a is 1, 2 or 3.

Specific examples of each of the reactive silicon groups of the polymer(B) include trimethoxysilyl, triethoxysilyl, tris(2-propenyloxy)silyl,triacethoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl,dimethoxyethylsilyl, (chloromethyl)dimethoxysilyl,(chloromethyl)diethoxysilyl, (methoxymethyl)dimethoxysilyl,(methoxymethyl)diethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl,and (N,N-diethylaminomethyl)diethoxysilyl groups. However, the reactivesilicon group is not limited thereto. Of these examples, preferred aremethyldimethoxysilyl, trimethoxysilyl, triethoxysilyl,(chloromethyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl,(methoxymethyl)diethoxysilyl, and (N,N-diethylaminomethyl)dimethoxysilylgroups since these groups show a high activity and can give a curedproduct good in mechanical properties. From the viewpoint of theactivity, particularly preferred are trimethoxysilyl,(chloromethyl)dimethoxysilyl, and (methoxymethyl)dimethoxysilyl groups.From the viewpoint of stability, particularly preferred aremethyldimethoxysilyl, methyldiethoxysilyl, and triethoxysilyl groups.From the viewpoint of safety, particularly preferred aremethyldiethoxysilyl, and triethoxysilyl groups. More preferred aretrimethoxysilyl, triethoxysilyl, and dimethoxymethylsilyl groups sincethe polymer (B) is easily produced.

The method for introducing the reactive silicon groups of the polymer(B) is not particularly limited. Reactive silicon groups may beintroduced into a polyoxyalkylene polymer having, at one terminal moietythereof, a terminal structure having two or more carbon-carbonunsaturated bonds, which is a polymer (A) of the present invention, soas to bond the reactive silicon groups to the unsaturated bonds. Thismethod is favorable since the method can easily have a purifying stepbefore the introduction of the reactive silicon groups to be high inpracticability, and can give a good-quality polymer (B) which keeps asufficient stability even when the polymer (B) is stored over a longterm. It is conceivable that a method for gaining the polymer (B) otherthan this method is, for example, a method of adding, for example, twoor more 3-glycidoxypropyltrimethoxysilane molecules thereto. In thiscase; however, an active terminal and a catalyst for the additionreaction unfavorably remain in the polymer to produce a tendency that apolymer good in stability is not easily obtained.

It is generally known that in a reaction for adding silyl groups toallyl groups through hydrosilylation reaction, the allyl groups areisomerized as a side reaction so that an internal olefin is produced. Itis therefore difficult to introduce reactive silicon groups into allylgroups in a proportion of 100%. In other words, when reactive silicongroups are introduced into a polymer having, at a terminal thereof, onlyone allyl group through hydrosilylation, it is difficult that thereactive silicon groups are introduced into all terminals of moleculesof the polymer in a proportion of 100%. Thus, in reaction for thereactive-silicon-group-containing polymer to be obtained, defects areinevitably generated. By contrast, when the polymer (A) of the presentinvention is used to yield the polymer (B) through hydrosilylation, thepolymer (B) which is a polymer having, at one or each terminal, one ormore silyl groups per terminal can be obtained since the polymer (A)has, at the terminal, plural allyl groups.

The terminal structure (concerned) of the polymer (B) is represented bythe following general formula (5):

In the formula, R¹, R², R³, R⁴, R⁵, Y, a and n are the same as describedabove, and the plural silicon groups are each independently selectable.

The method for introducing reactive silicon groups into the polymer (A)is not particularly limited, and may be a known method. Examples of theintroduction method are as follows:

(i) Hydrosilylation: the method is a method of adding a hydrosilanecompound to the unsaturated bonds through hydrosilylation reaction.

(ii) Reaction with a silane coupling agent: the method is a method ofcausing the polymer (A) to react with a compound having both of a groupcapable of reacting with an unsaturated bond to form a bond, and areactive silicon group (also called a silane coupling agent). An exampleof the silane coupling agent reactive with an unsaturated bond to form abond is a mercapto group.

The method (i) is favorable since the reaction is simple, and furtherthe amount of introduced reactive silicon groups is stably adjusted andphysical properties of the resultant reactive-silicon-group-containingpolymer are stable. The method (□) is favorable in that the method makesthe number of reaction options or choices large and makes it easy toheighten the proportion of introduced reactive silicon groups.

Some examples of the hydrosilane compound used in the method (i) are asfollows: halogenated silanes such as trichlorosilane,dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane,chloromethyldichlorosilane, dichloromethyldichlorosilane,bis(chloromethyl)chlorosilane, and methoxymethyldichlorosilane;alkoxysilanes such as trimethoxysilane, triethoxysilane,dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane,ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane,chloromethylmethylmethoxysilane, chloromethyldimethoxysilane,chloromethyldiethoxysilane, chloromethylmethoxymethylsilane,bis(chloromethyl)methoxysilane, methoxymethylmethylmethoxysilane,methoxymethyldimethoxysilane, methoxymethyldiethoxysilane,ethoxymethyldiethoxysilane, 3,3,3-trifluoropropyldimethoxysilane,N,N-diethylaminomethyldiethoxysilane,chloromethyldimethoxysilyloxydimethylsilane,chloromethyldiethoxysilyloxydimethylsilane,methoxymethyldimethoxysilyloxydimethylsilane,diethylaminomethyldimethoxysilyloxydimethylsilane, and3,3,3-trifluoropropyldimethoxysilyloxydimethylsilane; acyloxysilanessuch as diacetoxymethylsilane and diacethoxyphenylsilane; ketoxymatesilanes such as bis(dimethylketoxymate) methylsilane andbis(cyclohexylketoxymate) methylsilane; and isopropenyloxysilanes(acetone-eliminated type) such as triisopropenyloxysilane,chloromethyldiisopropenyloxysilane, andmethoxymethyldiisopropenyloxysilane.

About the use amount of the hydrosilane, the ratio by mole of thehydrosilane to unsaturated groups in a polymer that is a precursor (ofthe polymer (B)) (the ratio of the mole number of the hydrosilane tothat of the unsaturated groups) is preferably from 0.05 to 10 from theviewpoint of reactivity, and is preferably from 0.3 to 2 from theviewpoint of economic efficiency.

The hydrosilylation reaction is accelerated by various catalysts. Thecatalysts for hydrosilylation may be known catalysts, such as variouscomplexes each including cobalt, nickel, iridium, platinum, palladium,rhodium, ruthenium, or some other element. For example, the followingare usable: a catalyst in which platinum is carried on a carrier made ofalumina, silica or carbon black, and platinic chloride; a platinicchloride complex composed of platinic chloride and, e.g., an alcohol,aldehyde or ketone; a platinum-olefin complex [such asPt(CH₂═CH₂)₂(PPh₃), or Pt(CH₂═CH₂)₂Cl₂]; a platinum-vinylsiloxanecomplex [Pt{(vinyl)Me₂SiOSiMe₂(vinyl)} or Pt{Me(vinyl)SiO}₄}]; aplatinum-phosphine complex [Ph(PPh₃)₄, or Pt(PBu₃)₄]; and aplatinum-phosphate complex [Pt{P(OPh)₃}₄]. It is preferred from theviewpoint of reaction efficiency to use a platinum catalyst such asplatinic chloride, or a platinum vinylsiloxane complex. The temperaturecondition for the silylation reaction is not particularly limited. Inorder to lower the viscosity of the reaction system or improve thereactivity, the reaction is conducted preferably under heatingconditions, more preferably at a temperature of 50 to 150° C., inparticular preferably at a temperature of 70 to 120° C. If the reactiontime becomes longer than required, the polymer main chain may bedeteriorated. Thus, it is preferred to adjust the reaction time togetherwith the temperature. The temperature and the reaction time are affectedby the main chain structure of the polymer. For making the productionprocess efficient, the reaction is ended preferably in a period of 30minutes to 5 hours both inclusive, more preferably in a period of 3hours or shorter.

About the polymer (B), the content by percentage of the reactive silicongroups therein is large so that hydrolysis-condensation reaction of thereactive silicon groups advances simultaneously with thehydrosilylation. For such reasons, the polymer (B) may be increased inmolecular weight or may be increased in viscosity when stored over along term.

Thus, in the method for producing the polymer (B) throughhydrosilylation, the viscosity-increase and the storage stability of thepolymer (B) can be solved or improved by using a trialkylorthocarboxylate (E).

Specific examples of the trialkyl orthocarboxylate (E) include trimethylorthoformate, triethyl orthoformate, trimethyl orthoacetate, andtriethyl orthoacetate. Trimethyl orthoformate, and trimethylorthoacetate are more preferred.

The use amount of the trialkyl orthocarboxylate (E) is from 0.1 to 10parts by weight, preferably from 0.1 to 3 parts by weight for 100 partsby weight of the polymer (A). If the use amount is small, theadvantageous effects may not be sufficiently obtained to cause a rise inthe viscosity of the polymer (B). If the use amount is excessivelylarge, an economical disadvantage is caused and further work quantity isincreased for the step of removing the orthoester (E).

Examples of the silane coupling agent usable in the method (ii) includemercaptosilanes such as 3-mercaptopropyltrimethoxysilane,3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane,mercaptomethyltriethoxysilane, and mercaptomethyldimethoxymethylsinae.These silane coupling agents are mere examples. By using or applying asimilar reaction, a silyl group can be introduced.

About the main chain structure of the polymer (B), the same descriptionas about the polymer (A) are applicable to a preferred number-averagemolecular weight, molecular weight distribution, linear or branchedstructure, main chain species and method for producing various chainsthereof, and others.

The polymer(s) (A) and/or (B) of the present invention can be used as acurable composition. Hereinafter, a description will be made in detailabout a curable composition using the polymer(s) (A) and/or (B) obtainedaccording to the present invention.

The curable composition of the present invention contains, as one ormore essential components, the polymer (A) and/or the polymer (B), andmay contain a polymer having, at one terminal structure thereof, onecarbon-carbon unsaturated bond, and/or a polymer having, at one terminalstructure thereof, one reactive silicon group. The blend amount of theoptional polymer(s) is preferably from 1 to 200 parts by weight bothinclusive, more preferably from 10 to 100 parts by weight both inclusivefor 100 parts by weight of the total of the polymers (A) and (B).

The same description as about polymers (A) and (B) are applicable tostructures of the optional polymer(s) which are other than theterminated reactive group thereof, and methods for producing thepolymer(s).

The polymer having, at one terminal structure thereof, one carbon-carbonunsaturated bond preferably has a carbon-carbon unsaturated bond orcarbon-carbon unsaturated bonds which are from 0.5 to 3 both inclusivein number on average per molecule of the polymer. About the polymerhaving, at one terminal structure thereof, one carbon-carbon unsaturatedbond, the carbon-carbon unsaturated bond which the polymer has is, forexample, an allyl or methallyl group.

The polymer having, at one terminal structure thereof, one reactivesilicon group preferably has reactive silicon groups which are from 1.2to 3 both inclusive in number on average per molecule of the polymer.About the polymer having one reactive silicon group, the reactivesilicon group which the polymer has is, for example, a dimethoxymethyl,trimethoxysilyl or triethoxysilyl group.

About the polymer having, at one terminal structure thereof, onereactive silicon group, the following method (iii) is usable besides themethod (i) or (ii) as a method for introducing the reactive silicongroup to the polymer:

(iii) Reaction between the reactive-group-containing polymer and asilane coupling agent: the method is a method of causing a precursorpolymer having a reactive group, such as a hydroxyl group, an aminogroup or an unsaturated bond, to react with a compound having both of agroup capable of reacting with the reactive group to form a bond, and areactive silicon group (also called a silane coupling agent). Examplesof a combination of the reactive group of the precursor polymer and thereactive group of the silane coupling agent include a hydroxyl group andan isocyanate group, a hydroxyl group and an epoxy group, an amino groupand an isocyanate group, an amino group and a thioisocyanate group, anamino group and an epoxy group, an amino group and an acrylic structuresubjected to Michael addition to the group, and a carboxylate group andan epoxy group.

Examples of the silane coupling agent usable in the method (iii) are asfollows: isocyanatosilanes, which are reactive with a hydroxyl group,such as 3-isocyanatopropyltrimethoxysilane,3-isocyanatopropyldimethoxymethylsilane,3-isocyanatopropyltriethoxysilane,3-isocyanatopropyl(methoxymethyl)(methoxy) silane,isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, andisocyanatomethyldimethoxymethylsilane; epoxysilanes, which are reactivewith hydroxyl, amino and carboxylate groups, such as3-glycidoxypropyltrimethoxysilane,3-glycidoxypropyldimethoxymethylsilane,3-glycidoxypropyltriethoxysilane, glycidoxymethyltrimethoxysilane,3-glycidoxypropyl(methoxymethyl)(methoxy)methysilane,glycidoxymethyltriethoxysilane, andglycidoxymethyldimethoxymethylsilane; aminosilanes, which are reactivewith isocyanate and thioisocyanate groups, such as3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane,3-aminopropyltriethoxysilane,3-aminopropyl(methoxymethyl)(methoxy)methylsilane,3-(2-aminoethyl)propyltrimethoxysilane,3-(2-aminoethyl)propyldiethoxysilane,3-(2-aminoethyl)propyltriethoxysilane,3-(N-ethylamino)-2-methylpropyltrimethoxysilane,3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane,N-phenyl-3-aminopropyltrimethoxysilane,N-benzyl-3-aminopropyltrimethoxysilane,N-cyclohexylaminomethyltriethoxysilane,N-cyclohexylaminomethyldiethoxymethylsilane,N-phenylaminomethyltrimethoxysilane,(2-aminoethyl)aminomethyltrimethoxysilane,N,N′-bis[3-(trimethoxysilyl)propyl]ethylenediamine, andbis(3-(trimethoxysilyl)propyl)amine; (meth)acryloxysilanes, which arereactive with an amino group, such as3-(meth)acryloxypropyltrimethoxysilane,3-(meth)acryloxypropyltriethoxysilane,(meth)acryloxymethyltrimethoxysilane,(meth)acryloxymethyldimethoxymethylsilane, and(meth)acryloxymethyltriethoxysilane; and hydroxyalkylsilanes, such as3-hydroxypropyltrimethoxysilane and hydroxymethyltriethoxysilane. Thesesilane coupling agents are mere examples. By using or applying a similarreaction, a silyl group can be introduced.

The introduction of a silicon group according to the reaction of theseagents may be based on a direct reaction between the reactive groups ofthe polymer terminal and any one of the above-mentioned silanecompounds, or may make use of a multistep reaction using a reaction withan additional compound. Examples of the additional compound includecompounds having two or more reaction points, such as diisocyanatecompounds, primary amine compounds, and carbonate compounds.

As the composition of the present invention, the following is preferablyusable since the resultant cured product is good in balance betweenstretchability and strength to be favorably usable: a composition havinga polyoxyalkylene polymer (B1) having, at one terminal thereof, pluralreactive silicon groups, and a (meth)acrylate polymer (C) having one ormore reactive silicon groups. The reactive silicon group(s) of thepolymer (C) may be positioned at the terminal(s) of the polymeric mainchain, or in the middle of the main chain.

The (meth)acrylate monomer constituting the main chain of the(meth)acrylate polymer (C) having one or more reactive silicon groups isnot particularly limited, and may be various species. Specific examplesthereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl(meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate,isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl(meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate,n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl(meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl(meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate,(3-trimethoxysilyl)propyl (meth)acrylate, (3-dimethoxymethylsilyl)propyl(meth)acrylate, (2-trimethoxysilyl)ethyl (meth)acrylate,(2-dimethoxymethylsilyl)ethyl (meth)acrylate, trimethoxysilylmethyl(meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, an ethyleneoxide adduct of (meth)acrylic acid, trifluoromethylmethyl(meth)acrylate, 2-trifluoromethylethyl (meth)acrylate,2-perfluoroethylethyl (meth)acrylate,2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, perfluoroethylmethacrylate, trifluoromethyl (meth)acrylate, bis(trifluoromethyl)methyl(meth)acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth)acrylate,2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl(meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, and other(meth)acrylate monomers.

Examples of the monomer unit other than the above-mentioned monomersinclude acrylic acids such as acrylic acid and methacrylic acid; andmonomers each containing an amide group, such as N-methylolacrylamideand N-methylolmethacrylamide, monomers each containing an epoxy group,such as glycidyl acrylate and glycidyl methacrylate, and monomers eachcontaining a nitrogen-containing group, such as diethylaminoethylacrylate and diethylaminoethyl methacrylate.

The (meth)acrylate polymer (C) may a polymer obtained by copolymerizinga (meth)acrylate monomer with a vinyl monomer copolymerizable with thismonomer. The vinyl monomer is not particularly limited. Examples thereofinclude styrene monomers, such as styrene, vinyltoluene,α-methylstyrene, chlorostyrene, styrenesulfonic acid, and salts thereof;fluorine-containing vinyl monomers such as perfluoroethylene,perfluoropropylene, and vinylidene fluoride; silicon-containing vinylmonomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleicanhydride, maleic acid, and monoalkyl esters and dialkyl esters ofmaleic acid; fumaric acid, and monoalkyl esters and dialkyl esters offumaric acid; maleimide monomers such as maleimide, methylmaleimide,ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide,octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, andcyclohexylmaleimide; nitrile-group-containing vinyl monomers such asacrylonitrile and methacrylonitrile; amide-group-containing vinylmonomers such as acrylamide and methacrylamide; vinyl ester monomerssuch as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate,and vinyl cinnamate; alkenyl monomers such as ethylene and propylene;conjugated diene monomers such as butadiene and isoprene; and vinylchloride, vinylidene chloride, ally chloride, and allyl alcohol. Two ormore of these monomers are also usable as copolymerizable components.

Out of (meth)acrylate polymers obtained from these monomers, copolymerseach made from a styrene monomer and a (meth)acrylic acid monomer arepreferred since the copolymers are excellent in physical properties.More preferred are (meth)acrylate polymers each made from an acrylatemonomer and a methacrylate monomer. Particularly preferred are acrylatepolymers each made from an acrylate monomer.

The number of the reactive silicon group(s) of the polymer (C) permolecule thereof is preferably 1.0 to 5.0 on average. From the viewpointof mechanical properties obtained when the curable composition is cured,the number is more preferably 1.27 or more. From the viewpoint of thestability of the polymer (C), the number is more preferably 3.0 or less.

The method for introducing one or more reactive silicon groups into a(meth)acrylate polymer is not particularly limited, and may be, forexample, methods described below. (iv) A method of copolymerizing acompound having a polymerizable unsaturated group and areactive-silicon-containing group with any one of the above-mentionedmonomers; the use of this method produces a tendency that reactivesilicon groups are introduced at random into the main chain of thepolymer. (v) A method of using a mercaptosilane compound having areactive-silicon-containing group as a chain transfer agent topolymerize a (meth)acrylate polymer; the use of this method makes itpossible to introduce reactive silicon groups at a terminal of thepolymer. (vi) A method of copolymerizing a compound having apolymerizable unsaturated group and a reactive functional group (Vgroup), and then causing the resultant to react with a compound having afunctional group reactive with the reactive silicon group and with the Vgroup; specific examples of this method include a method ofcopolymerizing 2-hydroxyethyl acrylate, and then causing the hydroxylgroup of the resultant to react with an isocyanatosilane having areactive-silicon-containing group, and a method of copolymerizingglycidyl acrylate, and then causing the epoxy group of the resultant toreact with an aminosilane compound having a reactive-silicon-containinggroup. (vii) A method of modifying a terminated functional group of a(meth)acrylate polymer synthesized by living radical polymerization tointroduce a reactive silicon group thereinto. About the (meth)acrylatepolymer obtained by living radical polymerization, a functional group iseasily introduced into a terminal of the polymer. By modifying thisfunctional group, a reactive group can be introduced into the polymerterminal.

Examples of the silicon compound usable to introduce the functionalsilicon group(s) of the (meth)acrylate polymer (C) by use of theabove-mentioned methods are described hereinafter. Examples of thecompound used in the method (iv), which has a polymerizable unsaturatedgroup and a reactive silicon group, include 3-(trimethoxysilyl)propyl(meth)acrylate, 3-(dimethoxymethylsilyl)propyl (meth)acrylate,3-(triethoxysilyl)propyl (meth)acrylate, (trimethoxysilyl)methyl(meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate,(triethoxysilyl)methyl (meth)acrylate, (diethoxymethylsilyl)methyl(meth)acrylate, and 3-((methoxymethyl)dimethoxysilyl)propyl(meth)acrylate. From the viewpoint of availability, particularlypreferred are trimethoxysilylpropyl (meth)acrylate, and(dimethoxymetyl)propyl (meth)acrylate.

Examples of the mercaptosilane compound used in the method (v), whichhas a reactive-silicon-containing group, include3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane,3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane,(mercaptomethyl)dimethoxymethylsilane, andmercaptomethyltriethoxysilane.

Examples of the compound used in the method (vi), which has a reactivesilicon group and a V group, include isocyanatesilane compounds such as3-isocyanatopropyltrimethoxysilane,3-isocyanatopropyldimethoxymethylsilane,3-isocyanatopropyltriethoxysilane, isocyanatomethyltrimethoxysilane,isocyanatomethyltriethoxysilane, isocyanatomethyldimethoxymethylsilane,and isocyanatomethyldiethoxymethylsilane; epoxysilane compounds such as3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,3-glycidoxypropyldimethoxymethylsilane, glycidoxymethyltrimethoxysilane,glycidoxymethyltriethoxysilane, glycidoxymethyldimethoxymethylsilane,and glycidoxymethyldiethoxymethylsilane; and aminosilane compounds, suchas 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,3-aminopropyldimethoxymethylsilane, aminomethyltrimethoxysilane,aminomethyltriethoxysilane, aminomethyldimethoxymethylsilane,N-cyclohexylaminomethyltriethoxysilane,N-cyclohexylaminomethyldiethoxymethylsilane,N-phenylaminomethyltrimethylsilane, and(2-aminoethyl)aminomethyltrimethoxysilane.

In the method (vii), any modifying reaction is usable. For example, thefollowing method is usable therefor: a method of using a compound havinga functional group reactive with the terminated reactive group obtainedby polymerization, and a silicon group; or a method of using a compoundhaving a functional group reactive with the terminated reactive group,and a double bond to introduce a double bond into a terminal of thepolymer, and then introducing a reactive silicon group into this doublebond through hydrosilylation or some other reaction.

Two or more of these methods may be combined with each other at will. Inthe case of combining, for example, the methods (vi) and (v) with eachother, the polymer (C) that is a polymer having one or more reactivesilicon groups at a molecular chain terminal and/or a side chain thereofcan be obtained.

The reactive silicon group(s) of the polymer (C) is/are (each)represented by the following general formula (4):

—SiR⁵ _(3-a)Y_(a)  (4)

When the polymer (B1) is combined with the polymer (C) having one ormore reactive silicon groups (b3) (each) represented by the generalformula (4) in which a is 3, a cured product having a higher toughnessis obtained. The reactive silicon group(s) (b3) is/are (each) preferablya trimethoxysilyl or triethoxysilyl group.

The inventors have found out that when the polymer (B1) in the curablecomposition containing the polymer (B1) and the polymer (C) is apolyoxyalkylene polymer having both species of one or more reactivesilicon groups (b2) (each) represented by the general formula (4) inwhich a is 2, and one or more reactive silicon groups (b3) (each)represented by the general formula (4) in which a is 3, the resultantcured product is higher in strength. In the same manner, the inventorshave found out that also when the curable composition contains, asspecies of the polymer (B1), both of a polyoxyalkylene polymer havingone or more reactive silicon groups (b2) and a polyoxyalkylene polymerhaving one or more reactive silicon groups (b3), a cured product havinga far higher strength is obtained. The reactive silicon group(s) (b2)is/are (each) preferably a dimethoxymethylsilyl group, and the reactivesilicon group(s) (b3) is/are (each) preferably a trimethoxysilyl group.The method for producing the polymer (B1) having, in a single moleculethereof, the reactive silicon group(s) (b2) and the reactive silicongroup(s) (b3) may be, for example, a method of hydrosilylating apolyoxyalkylene having ally groups at both terminals thereof,respectively, with a mixture of trimethoxysilane anddimethoxymethylsilane.

It is general for those skilled in the art that the monomer compositionof the polymer (C) is selected in accordance with the usage and purpose(of the final product). For a usage about which strength is required,the glass transition temperature (Tg) is preferably relatively high. Thetemperature Tg is preferably from 0 to 200° C. both inclusive, morepreferably from 20 to 100° C. both inclusive. The temperature Tg isgained by Fox's equation described below.

Fox's equation:

1/(Tg(K))=Σ(Mi/Tgi)

wherein Mi represents the proportion by weight of a monomer component“i” which is a constituent element of a polymer, and Tgi represents theglass transition temperature (K) of a homopolymer made from the monomer“i”.

The number-average molecular weight of the polymer (C) is notparticularly limited, and is preferably from 500 to 100,000, morepreferably from 500 to 50,000, in particular preferably from 1,000 to30,000 in terms of that of polystyrene through GPC measurement.

Methods for blending the polymer (B1) with the polymer (C), which hasone or more reactive silicon groups, are suggested in JP-A-59-122541,JP-A-63-112642, JP-A-06-172631, JP-A-11-116763 and others. A differentmethod is also usable in which a (meth)acrylate monomer is polymerizedin the presence of a polyoxypropylene polymer having a reactive silicongroup. This producing method is specifically disclosed in JP-A-59-78223,JP-A-60-228516, JP-A-60-228517 and other publications. The polymer (B1)of the present invention can be blended with the polymer (C) by the samemethod. However, the blending method is not limited to these methods.

The blend ratio between the polymer (B1) and the polymer (C) is notparticularly limited. The ratio (by weight) of (B1) to (C) is preferablyfrom 95/5 to 10/90, more preferably from 80/20 to 20/80, in particularpreferably from 70/30 to 30/70. About each of the polymer (B1) of thepresent invention, and the polymer (C), only one species thereof may beused, or two or more species thereof may be used together.

In the present invention, a curable composition is usable which containsthe polymer (B) and a polymer (D) having a reactive silicon group orreactive silicon groups which are 0.5 or more and less than 1.2 innumber on average per molecule of the polymer (D). The combination ofthese two polymers makes it possible to adjust a balance between theviscosity of the curable composition and mechanical strengths of theresultant cured product.

The same description as about the polymer (A) is applicable to the mainchain structure of the polymer (D). The main chain structure ispreferably identical with that of the polymer (B). Moreover, the mainchain structure is preferably a polyoxyalkylene polymer.

When the polymer (B) is used together with the polymer (D), thenumber-average molecular weight of the polymer (B) is more preferablyfrom 5,000 to 50,000, in particular preferably from 10,000 to 35,000 interms of that of polystyrene through GPC. The number-average molecularweight of the polymer (D) is more preferably from 3,000 to 50,000, inparticular preferably from 3,000 to 10,000.

The molecular weight distribution of the polymer (D) is not particularlylimited, and is preferably less than 2.0, more preferably 1.6 or less,in particular preferably 1.4 or less, or 1.3 or less.

The reactive silicon group(s) of the polymer (D) can (each) berepresented by the following general formula (4):

—SiR⁵ _(3-a)Y_(a)  (4)

In order for the curable composition to supply, when cured, a rubberycured product having high mechanical properties, the lower limit and theupper limit of the number of the reactive silicon group(s) of thepolymer (D) are preferably 0.5 or more, and 1.2 or less, respectively,on average per molecule of the polymer (D). From the viewpoint of themechanical properties at the curing time, the lower limit and the upperlimit are more preferably 0.8 or more, and 1.0 or less, respectively.

The reactive silicon group(s) of the polymer (D) may be positioned atits molecular chain terminal(s), its side chain terminal(s), or boththereof. It is more preferred that the reactive silicon group(s) is/arepositioned, in particular, at the molecular chain terminal(s) since thebetween-crosslinking-point molecular weight becomes large so that arubbery cured product showing a high strength and a high elongation iseasily obtained.

The number on average of the reactive silicon groups in thereactive-silicon-group-containing polymer of the present invention isdefined as the number thereof on average that is measured by a method ofdetermining, quantitatively by high-resolution ¹H-NMR analysis, protonsonto which the reactive silicon groups are directly bonded. In thecalculation of the number on average of the reactive silicon group(s) inthe polymer (D), not only a precursor of the polymer which remains atthe time of introducing reactive silicon groups into the precursor, intowhich no reactive silicon group has been introduced, but also anyreactive-silicon-group-non-introduced polymer obtained by a sidereaction at this time are also regarded as parts of components of thepolymer (D), which has the same main chain structure as thesecomponents. The calculation is made under a condition that the number ofthese molecules is included into the population parameter (the number ofmolecules) when the number on average of the reactive silicon group(s)per molecule of the polymer (D) is calculated.

As far as the main chain structure of the polymer (D) satisfies arequirement that the reactive silicon group(s) per molecule is/are 0.5or more and less than 1.2 in number on average, the structure may be alinear or branched structure, or a structure having, at one terminalthereof, plural reactive silicon groups as represented by the generalformula (5). More preferred is a linear polymer in which reactivesilicon groups are introduced into only one terminal thereof. As far asthe main structure satisfies the requirement that the reactive silicongroup(s) per molecule is/are 0.5 or more and less than 1.2 in number onaverage, the main chain structure may be not made of a single species,and may be made of a mixture of polymers produced separately from eachother, or a mixture of polymers produced simultaneously.

The reactive silicon groups of the polymer (B) and the polymer (D) areselectable at will. It is preferred that the polymers (B) and (D) havethe same reactive silicon groups since physical properties of theresultant cured product are easily adjusted. The reactive silicon groupsare in particular preferably dimethoxysilyl groups.

The blend amount of the polymer (D) is more preferably from 1 to 100parts by weight both inclusive, more preferably from 10 to 50 parts byweight both inclusive for 100 parts by weight of the polymer (B).

The curable composition of the present invention may contain anorganopolysiloxane polymer (F) having a reactive silicon group. Thepolysiloxane is a polymer having a main chain in which a siloxane bondis repeated. An example thereof is polydimethylsiloxane. Thepolysiloxane may be a polysiloxane showing fluidity at normaltemperature. The polysiloxane may contain, as its main chain, adifferent polymer component such as a polyoxyalkylene. By the use of thepolysiloxane, it is expectable that the curable composition producesviscosity-decreasing and plasticizing effects. It is also expectablethat the composition is improved in low-temperature workability, and theresultant cured product is improved in surface tackiness, and iscontrolled about mechanical properties. The polysiloxane may have areactive silicon group. Examples of the reactive silicon group includedimethoxymethylsilyl, trimethoxysilyl, and triethoxysilyl groups. Theuse of such a polysiloxane may improve the cured product in strength.The blend amount of the polysiloxane is preferably from 1 to 100 partsby weight, more preferably from 5 to 50 part by weight, in particularpreferably from 10 to 30 parts by weight for 100 parts by weight of thepolymer (B).

In the present invention, a silanol condensing catalyst is used topromote hydrolysis/condensation reactions of the reactive silicon groupsof the polymers (B), (C), (D) and (F) to extend the chain of the(resultant) polymer or crosslink the polymer.

It is already known that many catalysts are usable as the silanolcondensing catalyst for the reactive-silicon-group-containing polymer.Examples thereof include an organic tin compound, a metal carboxylate,an amine compound, a carboxylic acid, an alkoxy metal, and an inorganicacid.

Specific examples of the organic tin compound include dibutyltindilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltindioctanoate, dibutyltin bis(2-ethylhexanoate), dibutyltinbis(methylmaleate), dibutyltin bis(ethylmaleate), dibutyltinbis(butylmaleate), dibutyltin bis(octylmaleate), dibutyltinbis(tridecylmaleate), dibutyltin bis(benzylmaleate), dibutyltindiacetate, dioctyltin bis(ethylmaleate), dioctyltin bis(octylmaleate),dibutyltin dimethoxide, dibutyltin bis(nonylphenoxide), dibutenyltinoxide, dibutyltin oxide, dibutyltin bis(acetylacetonate), dioctyltinbis(acetylacetonate), dibutyltin bis(ethylacetoacetonate), a reactionproduct made from dibutyltin oxide and a silicate compound, a reactionproduct made from dioctyltin oxide and a silicate compound, and areaction product made from dibutyltin oxide and a phthalate. From theviewpoint of an increase in interest in the environment in recent years,it is preferred to use a dioctyltin compound rather than any dibutyltincompound.

Specific examples of the metal carboxylate include tin carboxylates,lead carboxylates, bismuth carboxylates, potassium carboxylates, calciumcarboxylates, barium carboxylates, titanium carboxylates, zirconiumcarboxylates, hafnium carboxylates, vanadium carboxylates, manganesecarboxylates, iron carboxylates, cobalt carboxylates, nickelcarboxylates, and cerium carboxylates. The carboxylate group may be acombination of one out of carboxylic acids which will be described laterwith a metal that may be of various types. The metal species ispreferably bivalent tin, bismuth, bivalent iron, trivalent iron,zirconium, or titanium since the species is high in activity. Bivalenttin is most preferred.

Specific examples of the amine compound include aliphatic primary aminessuch as methylamine, ethylamine, propylamine, isopropylamine,butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine,nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine,stearylamine, and cyclohexylamine; aliphatic secondary amines such asdimethylamine, diethylamine, dipropylamine, diisopropylamine,dibutylamine, diamylamine, dihexylamine, dioctylamine,di(2-ethylhexyl)amine, didecylamine, dilaurylamine, dicetylamine,distearylamine, methylstearylamine, ethylstearylamine, andbutylstearylamine; aliphatic tertiary amines such as triamylamine,trihexylamine, and trioctylamine; aliphatic unsaturated amines such astriallylamine and oleylamine; aromatic amines such as aniline,laurylaniline, stearylaniline, and triphenylamine; nitrogen-containingheterocylic compounds such as pyridine, 2-aminopyridine,2-(dimethylamino)pyridine, 4-(dimethylaminopyridine), 2-hydroxypyridine,imidazole, 2-ethyl-4-methylimidazole, morpholine, N-methylmorpholine,piperidine, 2-piperidinemethanol, 2-(2-piperidino)ethanol, piperidone,1,2-dimethyl-1,4,5,6-tetrahydropyrimidine,1,8-diazabicyclo[5,4,0]undecene-7 (DBU),6-(dibutylamino)-1,8-diazabicyclo[5,4,0]undecene-7 (DBA-DBU),6-(2-hydroxypropyl)-1,8-diazabicyclo[5,4,0]undeca-7-ene (OH-DBU), acompound in which the OH group of OH-DBU is modified by urethanation orsome other, 1,5-diazabicyclo[4,3,0]nonene-5 (DBN),1,4-diazabicyclo[2,2,2]octane (DABCO), and aziridine; salts derived fromnitrogen-containing heterocylic compounds, such as a phenolic salt ofDBU (specifically, trade name: U-CAT SA1 (manufactured by San-AproLtd.), an octylate of DBU (specifically, trade name: U-CAT SA102(manufactured by San-Apro Ltd.)), a p-toluenesulfonate of DBU(specifically, trade name: U-CAT SA506 (manufactured by San-Apro Ltd.)),and an octylate of DBN (specifically, trade name: U-CAT 1102(manufactured by San-Apro Ltd.)); and other amines such asmonoethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine,ethylenediamine, propylenediamine, hexamethylenediamine,N-methyl-1,3-propanediamine, N,N′-dimethyl-1,3-propanediamine,diethylenetriamine, triethylenetetramine, 2-(2-aminoethylamino)ethanol,benzylamine, 3-methoxypropylamine, 3-lauryloxypropylamine,3-dimethylaminopropylamine, 3-diethylaminopropylamine,3-dibutylaminopropylamine, 3-morpholinopropylamine,2-(1-piperazinyl)ethylamine, xylylenediamine, and2,4,6-tris(dimethylaminomethyl)phenol; guanidines such as guanidine,phenylguanidine, and diphenylguanidine; and biguanides, such asbutylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide.

Of these examples, preferred are amidines such as1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBA-DBU, DBN and otheramidines; guanidines such as guanidine, phenylguanidine, anddiphenylguanidine; and biguanides such as butylbiguanide,1-o-tolylbiguanide, and 1-phenylbiguanide since these compounds show ahigh activity. Aryl-substituted biguanides such as 1-o-tolylbiguanideand 1-phenylbiguanide are preferred since it is expectable that theresultant product has a high adhesiveness.

Amine compounds show basicity. An amine compound about which the pKavalue of a conjugated acid thereof is 11 or more is preferred since thecatalyst activity is also high. Particularly preferred are1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBN and others sincethese compounds each show, as a pKa value of a conjugated acid thereof,a value of 12 or more to exhibit a high catalyst activity.

The amine compound used in the silanol condensing catalyst in thepresent invention may be an amino-group-containing silane coupling agent(referred to also as an aminosilane). One or more hydrolyzable groups ofthe aminosilane used as the silanol condensing catalyst in the presentinvention is/are (each) more preferably an alkoxy group such as amethoxy or ethoxy group, in particular preferably a methoxy or ethoxygroup since the group is mild in hydrolyzability to be easy to handle.Ethoxy and isopropenoxy groups are preferred from the viewpoint ofsafety since compounds eliminated therefrom by reaction are ethanol andacetone, respectively. The number of the hydrolyzable group(s) ispreferably 2 or more, in particular preferably 3 or more from theviewpoint of catalyst activity.

The silanol condensing catalyst may be a ketimine compound, from whichan amine compound as described above is produced by hydrolysis.

Specific examples of the above-mentioned carboxylic acid include aceticacid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid,stearic acid, oleic acid, linoleic acid, pivalic acid,2,2-dimethylbutyric acid, 2,2-diethylbutyric acid, 2,2-dimethylhexanoicacid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid,2-ethyl-2,5-dimethylhexanoic acid, neodeconoic acid, and versatic acid.2-Ethylhexanoic acid, neodeconoic acid, and versatic acid are preferredsince the acids are high in activity, and available. Derivatives ofthese carboxylic acids are also usable, examples thereof includingcarboxylic anhydrides, alkyl carboxylates, amides, nitriles, andhalogenated acyls.

Specific examples of the afore-mentioned alkoxy metal include titaniumcompounds such as tetrabutyl titanate, tetrapropyl titanate, titaniumtetrakis(acetylacetonate), diisopropoxytitanium bis(acetylacetonate),and diisopropoxytitanium bis(ethylacetoacetate); aluminum compounds suchas aluminum tris(acetylacetonate), aluminum tris(ethylacetoacetate),diisopropoxyaluminum ethylacetoacetate; zirconium compounds such aszirconium tetrakis(acetylacetonate); and hafnium compounds such astetrabutoxyhafnium.

Other examples of the silanol condensing catalyst include organicsulfonic acids such as trifluoromethanesulfonic acid; inorganic acidssuch as hydrochloric acid, phosphoric acid, and boronic acid;trifluoroboron complexes such as trifluorboron, a trifluoroborondiethylether complex, and a trifluoroboronethylamine complex;fluorine-anion-containing compounds such as ammonium fluoride,tetrabutylammonium fluoride, potassium fluoride, cesium fluoride,ammonium hydrogenfluoride, 1,1,2,3,3,3-hexafluoro-1-diethylaminopropane(MEC 81, popularly known as a Ishikawa reagent), potassiumhexafluorophosphate, Na₂SiF₆, K₂SiF₆, and (NH₄)₂SiF₆.

The silanol condensing catalyst may be also an optical acid generator oran optical base generator, which generates an acid or base by light.Examples of the optical acid generator include onium salt optical acidgenerators, such as triarylsulfonium salts such as p-phenylbenzylmethylsulfonium, p-hydroxyphenylbenzylmethyl sulfonium, triphenyl sulfonium,and diphenyl[4-(phenylthio)phenyl]sulfonium salts, and iodonium saltssuch as 4,4-bis[di(β-hydroxyethoxy)phenylsulfonio]phenylsulfidebishexafluoro antimonite, diphenyliodonium, bis(4-tert-butylphenyl)iodonium,(4-tert-butoxyphenyl)phenyliodonium, and (4-methoxyphenyl)phenyliodoniumsalts; sulfonic acid derivatives, such as benzoin tosylate, pyrrogalloltrimesylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate,N-(trifluoromethylsulfonyloxy)succinnimide,N-(trifluoromethylsulfonyloxy)phthalimide,N-(trifluoromethylsulfonyloxy)diphenylmaleide,N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,and N-(trifluoromethylsulfonyloxy)naphthylimide; diazomethanes, such asbis(trifluoromethylsulfonyl)diazomethane,bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane,bis(p-tolylsulfonyul)diazomethane, bis(2,4-xylylsulfonyl)diazomethane,bis(p-chlorophenylsulfonyl)diazomethane,methylsulfonyl-p-toluenesulfonyldiazomethane,cyclohexylsulfonyl(1,1-dimethylethylsulfonyl)diazomethane,bis(1,1-dimethylethylsulfonyl)diazomethane, andphenylsulfonyl(benzoyl)diazomethane; carboxylic acid esters; and ironarene complexes.

About the silanol condensing catalyst, two or more different catalystspecies may be used together. By using, for example, an amine compoundas described above together with a carboxylic acid, the combination cangain an effect of improving the reactivity. The catalyst activity isheightened also by using an acid such as a carboxylic acid with aphosphonium salt compound such as tetrabutylphosphonium hydroxide. Thereactivity may be improved by using a halogen-substituted aromaticcompound such as pentafluorophenyl or pentafluorobenzaldehyde togetherwith an amine compound.

The use amount of the silanol condensing catalyst is preferably from0.001 to 20 parts by weight, more preferably from 0.01 to 15 parts byweight, in particular preferably from 0.01 to 10 parts by weight for 100parts by weight of the total of the reactive-silicon-group-containingpolymer, that is, the polymers (A), (B), (C), (D) and (F). If the blendamount of the silanol condensing catalyst is less than 0.001 part byweight, the reaction rate may become insufficient. By contrast, if theblend amount of the silanol condensing catalyst is more than 20 parts byweight, the reaction rate is excessively large so that the period whenthe composition is usable becomes short. Thus, the composition tends tobe deteriorated in workability or storage stability. Furthermore, somesilanol condensing catalysts may each exude, after the curablecomposition is cured, onto the surface of the cured product or pollutethe curded product surface. In such a case, by setting the use amount ofthe silanol condensing catalyst into the range of 0.01 to 2.0 parts byweight, the composition keeps curability and further the surface stateof the cured product is kept good.

To the composition of the present invention may be added a silanecoupling agent, a reaction product of a silane coupling agent, or acompound other than any silane coupling agent as a tackifier.

Specific examples of the silane coupling agent includeamino-group-containing silanes such as γ-aminopropyltrimethoxysilane,γ-aminopropyltriethoxysilane, γ-aminopropyltris(2-propoxy)silane,γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane,N-β-aminoethyl-γ-aminopropyltrimethoxysilane,N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane,N-β-aminoethyl-γ-aminopropyltriethoxysilane,N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane,N-β-aminoethyl-γ-aminopropyltriisopropoxysilane,N-β-(β-aminoethyl)aminoethyl-γ-aminopropyltrimethoxysilane,N-6-aminohexyl-γ-aminopropyltrimethoxysilane,3-(N-ethylamino)-2-methylpropyltrimethoxysilane,γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane,N-phenyl-γ-aminopropyltrimethoxysilane,N-benzyl-γ-aminopropyltrimethoxysilane,N-vinylbenzyl-γ-aminopropyltriethoxysilane,N-cyclohexylaminomethyltriethoxysilane,N-cyclohexylaminomethyldiethoxymethylsilane,N-phenylaminomethyltrimethoxysilane,(2-aminoethyl)aminomethyltrimethoxysilane,(aminomethyl)dimethoxymethylsilane, (aminomethyl)trimethoxysilane,(phenylaminomethyl)dimethoxymethylsilane,(phenylaminomethyl)trimethoxysilane, bis(3-trimethoxysilylpropyl)amine,and N,N′-bis[3-(trimethoxysilyl)propyl]ethylenediamine;isocyanate-group-containing silanes such asγ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane,γ-isocyanatopropylmethyldiethoxysilane,γ-isocyanatopropylmethyldimethoxysilane,α-isocyanatomethyltrimethoxysilane, andα-isocyanatomethyldimethoxysilane; mercapto-group-containing silanessuch as γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane,and γ-mercaptopropylmethyldiethoxysilane; epoxy-group-containing silanessuch as γ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane andβ-(3,4-epoxycyclohexyl)ethyltriethoxysilane; carboxysilanes such asβ-carboxyethyltriethoxysilane,β-carboxyethylphenylbis(β-methoxyethoxy)silane andN-β-carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane;vinyl-type-unsaturated-group-containing silanes such asvinyltrimethoxysilane, vinyltriethoxysilane,γ-methacryloyloxypropylmethyldimethoxysilane, andγ-acryloyloxypropylmethyltriethoxysilane; halogen-containing silanessuch as γ-chloropropyltrimethoxysilane; isocyanurate silanes such astris(trimethoxysilyl) isocyanurate; carbamate silanes such as methyl(N-dimethoxymethylsilyl)carbamate, methyl(N-trimethoxysilylmethyl)carbamate, methyl(N-dimethoxymethylsilylpropyl)carbamate, and methyl(N-trimethoxysilylpropyl)carbamate; alkoxy-group-containing silanes suchas (methoxymethyl)dimethoxymethylsilane,(methoxymethyl)trimethoxysilane, (ethoxymethyl)trimethoxysilane, and(phenoxymethyl)trimethoxysilane; acid-anhydride-containing silanes suchas 3-(trimethoxysilyl)propylsuccinic anhydride, and3-(triethoxysilyl)propylsuccinic anhydride. Usable examples of thesilane coupling agent also include partially condensed products of thesesilanes, and derivatives obtained by modifying these silanes, such asamino-modified silyl polymers, silylated amino polymers, unsaturatedaminosilane complexes, phenylamino long-chain-alkyl silanes,aminosilylated silicones, and silylated polyesters.

These silane coupling agents may be used alone, or may be used in anycombination. Reaction products of various silane coupling agents arealso usable. Examples of the reaction products include reaction productseach made from an isocyanatosilane and a hydroxyl-group-containingcompound or an amino-group-containing compound; reaction products eachmade from an aminosilane and an acrylic-group-containing compound or amethacrylic-group-containing compound (Michael addition reactionproducts); reaction products each made from an aminosilane and anepoxy-group-containing compound; and reaction products each made from anepoxysilane and a carboxylic-acid-group-containing compound or anamino-group-containing compound. Usable examples of the silane couplingagent also include reaction products each made from silane couplingagents such as an isocyanatosilane and an aminosilane, an aminosilaneand a (meth)acrylic-group-containing silane, an aminosilane and anepoxysilane, and an aminosilane and an acid-anhydride-containing silane.

The use amount of the silane coupling agent is preferably from 0.1 to 20parts by weight, in particular preferably from 0.5 to 10 parts by weightfor 100 parts by weight of the whole of thereactive-silicon-group-containing polymer.

Specific examples of the tackifier other than silane coupling agentsinclude epoxy resin, phenol resin, sulfur, alkyl titanate, and aromaticpolyisocyanates although the tackifier is not particularly limitedthereto. About the tackifier, only a single species thereof may be used,or two or more species thereof may be used in a mixture form. Theaddition of the tackifier (to the composition) makes it possible toimprove the composition in adhesiveness to an adherend.

A plasticizer may be added to the composition of the present invention.The addition of the plasticizer makes it possible to adjust theviscosity and the slump property of the composition, and mechanicalproperties of a cured product obtained by curing the curablecomposition, such as the hardness, the tensile strength and theelongation thereof. Specific examples of the plasticizer includephthalate compounds such as dibutyl phthalate, diisononyl phthalate(DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecylphthalate (DIDP), butylbenzyl phthalate; terephthalate compounds such asbis(2-ethylhexyl)-1,4-benzenedicarboxylate (specifically, trade name:EASTMAN 168 (manufactured by Eastman Chemical Co.)); non-phthalatecompounds such as diisononyl 1,2-cylohexanedicarboxylate (specifically,trade name: Hexamoll DINCH (manufactured by BASF Corp.); polyhydricaliphatic carboxylic acids such as dioctyl adipate, dioctyl sebacate,dibutyl sebacate, diisodecyl succinate, and tributyl acetylcitrate;unsaturated aliphatic acid ester compounds such as butyl oleate andmethyl acetylricinoleate; phenyl alkylsulfonates (specifically, tradename: Mesamoll (manufactured by Lanxess AG); phosphate compounds such astricresyl phosphate and tributyl phosphate; trimellitate compounds;chlorinated paraffin; alkyldiphenyls, partially hydrogenated terphenyl,and other hydrocarbon oils; process oil; epoxidized soybean oil, benzylepoxystearate, and other epoxy plasticizers.

A polymeric plasticizer is also usable. The use of the polymericplasticizer makes it possible to cause the cured product to maintaininitial properties over a longer term than the use of anylow-molecular-weight plasticizer. The use also makes it possible toimprove the dryability (paintability) of an alkyd paint painted onto thecured product. Specific examples of the polymeric plasticizer includevinyl polymers obtained by polymerizing a vinyl monomer by variousmethods; esters of a polyalkylene, such as diethylene glycol dibenzoate,triethylene glycol dibenzoate, and pentaerythritol esters; polyesterplasticizers each obtained from a dibasic acid, such as sebacic acid,adipic acid, azelaic acid or phthalic acid, and a dihydric alcohol, suchas ethylene glycol, diethylene glycol, triethylene glycol, propyleneglycol or dipropylene glycol; polyethers, such as polyethylene glycolpolypropylene glycol having a number-average molecular weight of 500 ormore, or 1,000 or more, polytetramethylene glycol, any otherpolyetherpolyol, or derivatives each obtained by converting hydroxylgroups of such a polyetherpolyol into ester groups or ether groups;polystyrenes such as polystyrene, and poly-α-methylstyrene; andpolybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, andpolychloroprene. A physical property can be given to various polymers bycopolymerizing one or more monomers therefor with areactive-group-containing monomer. For example, it is known that by useof, for example, a polybutadiene into which a maleic acid is grafted,the curable composition or the cured product is improved inadhesiveness-improving effect or elastic recovery factor.

Of these polymeric plasticizers, plasticizers compatible with thepolymer (B) are preferred. From this viewpoint, polyether polymers arepreferred. The use of a polyether polymer as the plasticizer favorablyimproves the curable composition in surface curability and depthcurability, and causes no curing delay after the composition is stored.Of the polyether polymers, polypropylene glycol is more preferred. Inthe case of using a plasticizer having a functional group, such as ahydroxyl group, for example, polypropylene glycol, the curablecomposition may be lowered in curability when stored, and the curedproduct may be lowered in mechanical properties. However, these problemscan be solved, using a compound in which the hydroxyl group is convertedinto, for example, an alkoxy group. For example, a polypropylene glycolthe hydroxyl groups of which have been substituted with allyl groups ispreferred since this compound is easily produced. From the viewpoint ofcompatibility, weather resistance, and heat resistance, vinyl polymersare preferred. Of the vinyl polymers, particularly preferred are acrylicpolymers such as polyalkyl (meth)acrylates. The method for synthesizingthe polymers is preferably living radical polymerization, morepreferably atom transfer radical polymerization since the resultantpolymer can be narrow in molecular weight distribution and be made lowin viscosity. It is also preferred to use a polymer obtained through theso-called SGO process, in which an alkyl (meth)acrylate monomer issubjected to continuous bulk polymerization at high temperature and highpressure, as described in JP-A-2001-207157.

The number-average molecular weight of the polymeric plasticizer ispreferably from 500 to 15,000, more preferably from 800 to 10,000, evenmore preferably from 1,000 to 8,000, in particular preferably from 1,000to 5,000, most preferably from 1,000 to 3,000. If the molecular weightis excessively low, the plasticizer elutes out with time by heat orrainfall so that the curable composition or the cured product cannotmaintain initial properties over a long term. If the molecular weight isexcessively high, the plasticizer is high in viscosity to bedeteriorated in workability.

The molecular weight distribution of the polymeric plasticizer is notparticularly limited, and is preferably narrow to be less than 1.80. Themolecular weight distribution is more preferably 1.70 or less, even morepreferably 1.60 or less, even more preferably 1.50 or less, inparticular 1.40 or less, most preferably 1.30 or less.

The number-average molecular weight of the polymeric plasticizer ismeasured by GPC when the plasticizer is a vinyl polymer, and is measuredby terminated group analysis when the plasticizer is a polyetherpolymer. The molecular weight distribution (Mw/Mn) is measured by GPC(in terms of that of polystyrene).

The use amount of the plasticizer is preferably from 5 to 150 parts byweight, more preferably from 10 to 120 parts by weight, in particularfrom 20 to 100 parts by weight for 100 parts by weight of the total ofthe polymers (A), (B), (C), (D) and (F). If the use amount is less than5 parts by weight, the plasticizer comes not to exhibit an advantageouseffect thereof. If the amount is more than 150 parts by weight, thecured product is insufficient in mechanical strengths. About theplasticizer, a single species thereof may be used alone, or two or morespecies thereof may be used together. A low molecular weight plasticizerand a polymeric plasticizer may be used together. When a polymer isproduced, the plasticizer(s) may be blended thereinto.

To the composition of the present invention may be added a solvent ordiluting agent. The solvent and the diluting agent are not particularlylimited, and may each be, for example, an aliphatic hydrocarbon, anaromatic hydrocarbon, an alicyclic hydrocarbon, a halogenatedhydrocarbon, an alcohol, an ester, a ketone, or an ether. When thesolvent or diluting agent is used, the boiling point of the solvent ispreferably 150° C. or higher, more preferably 200° C. or higher, inparticular preferably 250° C. or higher against a problem of airpollution when the composition is used indoors. About the solvent ordiluting agent, a single species thereof may be used alone, or two ormore species thereof may be used together.

To the composition of the present invention may be added a silicate. Thesilicate acts as a crosslinking agent to have a function of improving acured product obtained from the curable composition of the presentinvention in restorability, endurance and creep resistance. The silicatealso has an advantageous effect of improving the composition inadhesiveness and water-resistant adhesiveness, and the cured product inadhesion durability under high temperature and high humidity. Thesilicate may be a tetraalkoxysilane or alkylalkoxysilane, or a partiallyhydrolyzed condensate of the silane.

Specific examples of the silicate include tetramethoxyisilane,tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane,methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane,tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, andother tetraalkoxysilanes (tetraalkyl silicates); and respectivepartially hydrolyzed condensates of these compounds.

The partially hydrolyzed condensate of the tetraalkoxysilane is morepreferred since the compound produces a larger advantageous effect ofimproving the restorability, durability, and creep resistance in thepresent invention than the tetraalkoxysilane.

The partially hydrolyzed condensate of the tetraalkoxysilane is, forexample, a compound obtained by adding water to the tetraalkoxysilane inan ordinary manner, and then hydrolyzing the resultant partially to becondensed. The partially hydrolyzed condensate of the organosilicatecompound may be a commercially available product. Examples of such acondensate include products, METHYL SILICATE 51 and ETHYL SILICATE 40(manufactured by Colcoat Co., Ltd.).

When the silicate is used, the use amount thereof is from 0.1 to 20parts by weight, preferably from 0.5 to 10 parts by weight for 100 partsby weight of the total of the polymers (A), (B), (C), (D) and (F).

Various fillers may be blended into the composition of the presentinvention. Examples of the fillers include reinforcing fillers such asfumed silica, precipitated silica, crystalline silica, fused silica,dolomite, silicic anhydrate, hydrated silicic acid, and carbon black;heavy calcium carbonate, colloidal calcium carbonate, magnesiumcarbonate, diatomaceous earth, calcinated clay, clay, talc, titaniumoxide, bentonite, organic bentonite, ferric oxide, fine aluminum powder,flint powder, zinc oxide, active zinc flower, and resin powders such asPVC powder and PMMA powder; and asbestos, glass fiber, filaments, andother fibrous fillers.

As described in JP-A-2001-181532, it is allowable to mix the fillerevenly with a dehydrating agent such as calcium oxide, seal the mixtureinto a bag made of an airtight material, and then allow the bag to standstill for an appropriate period to dehydrate and dry the filler. Whenthe composition of the present invention is rendered a one-pack typecomposition, the use of this low-water-content filler makes it possibleto improve the composition in storage stability.

When a composition high in transparency is obtained, the following isusable as the filler, as described in JP-A-11-302527: a polymericpowder, the raw material of which is a polymer made from, for example,methyl (meth)acrylate; or amorphous silica. Moreover, the compositionhigh in transparency can be obtained by using, as the filler, forexample, hydrophobic silica, which is fine silica dioxide powder havinga surface to which hydrophobic groups are bonded, as described inJP-A-2000-38560. The surface of fine silicon dioxide powder is generallymade of silanol groups (—SiOH). Hydrophobic silica is a substance inwhich an organic silicon halide compound, an alcohol or the like iscaused to react with the silanol groups to produce “—SiO-hydrophobicgroups”. Specifically, hydrophobic silica is a substance obtained bycausing, for example, dimethylsiloxane, hexamethyldisilazane,dimethyldichlorosilane, trimethoxyoctylsilane, or trimethylsilane toreact with silanol groups present on the surface of fine silicon dioxidepowder. For reference, fine silicon dioxide powder having a surface madeof silanol groups (—SiOH) is called fine hydrophilic silica powder.

In the case of desiring to yield a cured product high in strength usingsuch a filler, it is preferred to use a filler selected from fumedsilica, precipitated silica, crystalline silica, fused silica, dolomite,silicic anhydrate, hydrated silicic acid, carbon black, surface-treatedfine calcium carbonate, calcinated clay, clay, and active zinc flower. Anano filler having a particle diameter of about 1 to 100 nm is alsousable. The use amount thereof is preferably from 1 to 200 parts byweight for 100 parts by weight of the total of the polymers (A), (B),(C), (D) and (F).

In the case of desiring to yield a cured product low in strength andlarge in breaking elongation, a favorable result is obtained mainly byusing a filler selected from titanium oxide, heavy calcium carbonate,other calcium carbonate species, magnesium carbonate, talc, ferricoxide, zinc oxide, volcanic soil balloons, and others in an amount of 5to 200 parts by weight for 100 parts by weight of the polymers (A), (B),(C), (D) and (F). As calcium carbonate is larger in specific surfacearea, the resultant cured product is in general more largely improved inbreaking strength, breaking elongation, and adhesiveness. In the case ofusing calcium carbonate, it is desired to use surface-treated finecalcium carbonate together with a calcium carbonate species large inparticle diameter, such as heavy calcium carbonate. The particlediameter of the surface-treated fine calcium carbonate is preferably 0.5μm or less. The surface treatment is preferably conducted with analiphatic acid or an aliphatic acid salt. The particle diameter of thecalcium carbonate species large in particle diameter is preferably 1 μmor more, and a non-surface-treated species is usable as this species.Examples of a surface treating agent for producing the surface-treatedcalcium carbonate powder include aliphatic acids and unsaturatedaliphatic acids, typically, palmitic acid, caprylic acid, capric acid,lauric acid, stearic acid, arachidic acid, behenic acid, lignocericacid, oleic acid, linoleic acid and linolenic acid; rosin acid compoundsand other carboxylic acids, and esters thereof; silane compounds such ashexamethyldisilazane, chlorosilane, and aminosilane; and paraffincompounds. However, the surface treating agent is not limited to thesecompounds. It is preferred that the surface treating agent is acarboxylic acid out of these examples since in the case of preparing acurable silicon resin composition, curing delay is less easily caused.The carboxylic acid is in particular preferably a saturated aliphaticacid or unsaturated aliphatic acid since the curing delay is even lesseasily caused. Of course, these fillers may be used alone or in the formof a mixture of two or more thereof. It is allowable to use analiphatic-acid-surface-treated colloidal calcium carbonate together witha calcium carbonate species having a particle diameter of 1 μm or more,such as non-surface-treated heavy calcium carbonate.

The use amount of the filler is preferably from 1 to 300 parts byweight, in particular preferably from 10 to 200 parts by weight for 100parts by weight of the total of the polymers (A), (B), (C), (D) and (F).

In order to improve the composition in workabilities (such asanti-dripping property) or make the surface of the cured product into amat or delustered state, it is preferred to add organic balloons orinorganic balloons thereto. These fillers may be surface-treated. Aboutthese fillers, only one species thereof may be used, or two or morespecies thereof may be used in a mixture form. For the improvement inthe workabilities (such as the anti-dripping property), the particlediameter of the balloons is preferably 0.1 mm or less. In order to makethe cured product surface mat, the particle diameter is preferably from5 to 300 μm.

The composition of the present invention is favorably used for jointsfor sizing boards, in particular, ceramic sizing boards, and otherhousing external walls; an adhesive for external wall tiles; and anadhesive for external wall tiles that remains as it is in joints betweenthe tiles; and others. It is desired that the design of the externalwalls is matched with that of the sealing material. In particular, asthe external walls, high-quality external walls based on sputteringpaint, the incorporation of aggregates, or some other treatment havebeen being used. When the composition of the present invention is acomposition with which a substance in the form of scales or granuleshaving a diameter of 0.1 mm or more, preferably from about 0.1 to 5.0 mmis blended, this composition is an excellent composition which gives acured product matchable with such high-quality external walls and isexcellent in chemical resistance. Thus, the external appearance of thiscured product sustains over a long term. By use of the granularsubstance, the surface of the cured product comes to have a coarse feelin a scattered sand tone or sandstone tone. By use of the scalysubstance, the composition comes to have an irregular surface resultingfrom the scaly form.

As described in JP-A-09-53063, preferred examples of the diameter, theblend amount, the material and others of the scaly or granular substanceare as follows: The diameter is 0.1 mm or more, preferably from about0.1 to 5.0 mm, and may be an appropriate diameter matchable with thematerial, the pattern and others of the external walls. The diameter maybe from about 0.2 to 5.0 mm, or from about 0.5 to 5.0 mm. About thescaly substance, the thickness is set into the range of about 1/10 to ⅕of the diameter (thickness: about 0.01 to 1.00 mm). The scaly orgranular substance is beforehand blended into the main sealing material,and then carried as a sealing material to an application spot, or thesubstance is blended into the main sealing material in an applicationspot when used.

The scaly or granular substance is blended in an amount of about 1 to200 parts by weight for 100 parts by weight of the composition for asealing material, an adhesive or some other. The blend amount isappropriately selected in accordance with the size of individual piecesor granules of the scaly or granular substance, the material and thepattern of the external walls, and other factors.

The scaly or granular substance may be a natural substance such assilica sand or mica, a synthetic rubber, a synthetic resin, or aninorganic substance such as alumina. The substance is colored into anappropriate color in accordance with the material and the pattern of theexternal walls, and other factors in order to be improved in designproperty when filled into a joint region (between the walls).

Preferred examples of the method for finishing the curable compositionor the cured product, and others are described in JP-A-09-53063.

For the same purpose, balloons (preferably, balloons having an averageparticle diameter of 0.1 mm or more) may be used; in this case, thesurface of the cured product comes to have a coarse feeling in ascattered sand tone or sandstone tone, and further the product can bemade light. Preferred examples of the diameter, the blend amount, thematerial and others of the balloons are as described in JP-A-10-251618.

The balloons are spherical fillers having a hollow inside. The balloonsmay be added to make the composition light (make the specific gravitythereof low). Examples of the material of the balloons include inorganicmaterials such as glass, volcanic soil, and silica; and organicmaterials such as phenol resin, urea resin, polystyrene, and saran. Thematerial is not limited to only these materials. Thus, an inorganicmaterial and an organic material may be composited with each other, orlaminated onto each other to form plural layers. Inorganic balloons,inorganic balloons, or balloons in which, for example, these arecomposited with each other are usable. The used balloons may be composedof the same balloon species, or of a mixture in which different balloonspecies are mixed with each other. The balloons may be surface-processedor surface-coated balloons, or balloons surface-treated with a surfacetreating agent that may be of various types. Examples thereof includeorganic balloons coated with, for example, calcium carbonate, talc ortitanium oxide, and inorganic balloons surface-treated with a silanecoupling agent.

In order for the surface to gain a coarse feeling in a scattered sandtone or sandstone tone, the particle diameter of the balloons ispreferably 0.1 mm or more. The particle diameter may be from about 0.2to 5.0 mm, or from about 0.5 to 5.0 mm. If the particle diameter is lessthan 0.1 mm, the composition is merely raised in viscosity even by theincorporation of a large proportion of the balloons, so that the coarsefeeling may not be exhibited. The blend amount of the balloons caneasily be decided in accordance with a target degree of the coarsefeeling in the scattered sand tone or sandstone tone. It is usuallydesired to incorporate balloons having a particle diameter of 0.1 mm ormore into the composition in a concentration of 5 to 25% by volume ofthe composition. If the concentration by volume of the balloons is lessthan 5% by volume, no coarse feeling is produced. If the concentrationis more than 25% by volume, the sealing material or adhesive is high inviscosity to be deteriorated in workability, and the cured product isalso high in modulus. In short, basic performances of the sealingmaterial or adhesive tend to be damaged. The concentration by volume ofthe sealing material is in particular preferably from 8 to 22% by volumefor a balance between the basic performances of the sealing material.

When the balloons are used, the following may be added (to thecomposition): a slip inhibitor as described in JP-A-2000-154368; or anamine compound for making the surface of the cured product into a matstate as well as in the irregularity state, in particular, a primaryamine and/or a secondary amine having a melting point of 35° C. orhigher, as described in JP-A-2001-164237.

Specific examples of the balloons are described in JP-A-02-129262,JP-A-04-8788, JP-A-04-173867, JP-A-05-1225, JP-A-07-113073,JP-A-09-53063, JP-A-10-251618, JP-A-2000-154368 and JP-A-2001-164237, WO97/05201, and other publications.

Thermally expansible fine hollow particles are usable, which aredescribed in JP-A-2004-51701, JP-A-2004-66749, and others. The thermallyexpansible fine hollow particles are each a plastic sphere in which alow-boiling-point compound, such as a hydrocarbon having 1 to 5 carbonatoms, is wrapped into a spherical form with a polymeric shell material(vinylidene chloride based copolymer, acrylonitrile based copolymer, orvinylidene chloride-acrylonitrile copolymer). By heating a bondingregion using the present composition, the pressure of a gas inside theshells of the thermally expansible fine hollow particles is increased tosoften the polymeric shell material, so that the particles aredrastically increased in volume. Thus, a function of peeling the bondinginterfaces from each other is fulfilled. The addition of the thermallyexpansible fine hollow particles makes it possible to yield, withoutusing any organic solvent, an adhesive composition peelable by heating.The composition is a composition that can easily be peeled only byheating, without breaking the material of the composition, when thecomposition is unnecessary.

Also when the composition of the present invention containssealing-material-cured particles, irregularities are formed in thesurface of the cured product. Thus, the cured product can be improved indesign property. As described in JP-A-2001-115142, preferred examples ofthe diameter, the blend amount, the material and others of thesealing-material-cured particles are as follows: The diameter ispreferably from about 0.1 to 1 mm, more preferably from about 0.2 to 0.5mm. The blend amount is preferably from 5 to 100% by weight, morepreferably from 20 to 50% by weight of the composition. Examples of thematerial include urethane resins, silicone resins, modified silicones,and polysulfide rubbers. The material is not limited as far as thematerial is a material usable for sealing material. A sealing materialof a modified silicone type is preferred.

A drip inhibitor may be optionally added to the composition of thepresent invention to prevent the composition from dripping to make theworkability thereof good. The drip inhibitor is not particularlylimited. Examples thereof include polyamide waxes; hydrogenated castoroil derivatives; and metal soaps such as calcium stearate, aluminumstearate, and barium stearate. A composition high in thixotropy and goodin workability is obtained, using a rubber powder having a particlediameter of 10 to 500 μm as described in JP-A-11-349916, or an organicfiber as described in JP-A-2003-155389. These drip inhibitors may beused alone, or in any combination of two or more thereof.

The use amount of the drip inhibitor is preferably from 0.1 to 20 partsby weight for 100 parts by weight of the total of polymers (A), (B),(C), (D) and (F).

An antioxidant (anti-ageing agent) is usable in the composition of thepresent invention. The use of the antioxidant makes it possible toheighten the cured product in weather resistance. Examples of theantioxidant include hindered phenolic, monophenolic, bisphenolic, andpolyphenolic antioxidants. The hindered phenolic antioxidants areparticularly preferred. Equivalently, a hindered amine light stabilizeris usable, examples thereof including TINUVIN 622LD, TINUVIN 144,CHIMASSORB 944LD, and CHIMASSORB 119FL (each manufactured by Ciba JapanK.K.); ADEKASTAB LA-57, ADEKASTAB LA-62, ADEKASTAB LA-67, ADEKASTABLA-63, and ADEKASTAB LA-68 (each manufactured by Adeka Corp.); and SANOLLS-770, SANOL LS-765, SANOL LS-292, SANOL LS-2626, SANOL LS-1114, andSANOL LS-744 (each manufactured by Sankyo Lifetech Co., Ltd.). Specificexamples of the antioxidant are also described in JP-A-04-283259 andJP-A-09-194731.

The use amount of the antioxidant is preferably from 0.1 to 10 parts byweight, in particular preferably from 0.2 to 5 parts by weight for 100parts by weight of the total of the polymers (A), (B), (C), (D) and (F).

A light stabilizer is usable in the composition of the presentinvention. The use of the light stabilizer makes it possible to preventthe cured product from being deteriorated by optical oxidization.Examples of the light stabilizer include benzotriazole, hindered amine,and benzoate compounds. The hindered amine compounds are particularlypreferred.

The use amount of the light stabilizer is preferably from 0.1 to 10parts by weight, in particular preferably from 0.2 to 5 parts by weightfor 100 parts by weight of the polymers (A), (B), (C), (D) and (F).

When an optically curable substance is blended into the composition ofthe present invention and, in particular, an unsaturated acryliccompound is used as this substance, it is preferred to use, as ahindered amine light stabilizer, a tertiary-amine-containing hinderedamine light stabilizer as described in JP-A-05-70531 in order to improvethe composition in storage stability. Examples of thetertiary-amine-containing hindered amine light stabilizer include lightstabilizers such as TINUVIN 622LD, TINUVIN 144, and CHIMASSORB 119FL(each manufactured by Ciba Japan K.K.); ADEKASTAB LA-57, ADEKASTABLA-62, ADEKASTAB LA-67, and ADEKASTAB LA-63 (each manufactured by AdekaCorp.); and SANOL LS-765, SANOL LS-292, SANOL LS-2626, SANOL LS-1114,and SANOL LS-744 (each manufactured by Sankyo Lifetech Co., Ltd.).

An ultraviolet absorbent is usable in the composition of the presentinvention. The use of the ultraviolet absorbent makes it possible toheighten the cured product in surface weather resistance. Examples ofthe ultraviolet absorbent include benzophenone, benzotriazole,salicylate, substituted tolyl, and metal chelate compounds. Thebenzotriazole compounds are particularly preferred, and examples thereofinclude TINUVIN P, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 327,TINUVIN 328, TINUVIN 329, and TINUVIN 571 (each manufactured by CibaJapan K.K.). Particularly preferred are2-(2H-1,2,3-benzotriazole-2-yl)-phenolic compounds. It is preferred touse a phenolic or hindered phenolic antioxidant, a hindered amine lightstabilizer, and a benzotriazole ultraviolet absorbent together.

The use amount of the ultraviolet absorbent is preferably from 0.1 to 10parts by weight, in particular from 0.2 to 5 parts by weight for 100parts by weight of the total of the polymers (A), (B), (C), (D) and (F).

A physical property adjustor may be optionally added to the curablecomposition of the present invention to adjust tensile properties of theresultant cured product. The physical property adjustor is notparticularly limited. Examples thereof include alkylalkoxysilanes suchas phenoxytrimethylsilane, methyltrimethoxysilane,dimethyldimethoxysilane, trimethylmethoxysilane, andn-propyltrimethoxysilane; arylalkoxysilanes such asdiphenyldimethoxysilane and phenyltrimethoxysilane;alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane,methyltriisopropenoxysilane, andγ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilyl borates suchas tris(trimethylsilyl) borate and tris(triethylsilyl) borate; siliconevanishes; and polysiloxanes. The use of the physical property adjustormakes it possible to raise the hardness obtained when the composition ofthe present invention is cured, or contrarily lower the hardness toexhibit breaking elongation. The above-mentioned physical propertyadjustors may be used alone, or in any combination of two or morethereof.

In particular, a compound which undergoes hydrolysis to produce acompound having, in the molecule thereof, a monovalent silanol group hasan effect of lowering the modulus of the cured product withoutdeteriorating the stickiness of the cured product. Particularlypreferred is a compound which produces trimethylsilanol. Examples of thecompound which undergoes hydrolysis to produce a compound having, in themolecule thereof, a monovalent silanol group are described inJP-A-05-117521. Other examples thereof include any compound that is aderivative of an alkylalcohol such as hexanol, octanol or decanol, andthat undergoes hydrolysis to produce a silicon compound which produces asilane monool such as trimethylsilanol; and any compound that is aderivative of a polyhydric alcohol having 3 or more hydroxyl groups,such as trimethylolpropane, glycerin, pentaerythritol or sorbitol, andthat undergoes hydrolysis to produce a silicon compound which produces asilane monool, as described in JP-A-11-241029.

Other examples thereof include any compound that is a derivative of anoxypropylene polymer, and that undergoes hydrolysis to produce a siliconcompound which produces a silane monool, as described in JP-A-07-258534;and any organic polymer having a crosslinkable and hydrolyzablesilicon-containing group, and a silicon-containing group that canundergo hydrolysis to be converted to a monosilanol-containing compound,as described in JP-A-06-279693.

The compound having an effect of lowering the modulus of the curedproduct may be a trialkylsilyl borate, such as tris(trimethylsily)borate or tris(triethylsilyl) borate.

A tackifier may be added to the present invention to heighten thecomposition in adhesiveness or adhesiveness onto a substrate, or attaina different required purpose. The tackifier is not particularly limited,and may be an ordinarily used tackifier.

Specific examples thereof include terpene resin, aromatic modifiedterpene resin and hydrogenated terpene resin obtained by hydrogenatingthis resin, terpene-phenol resin obtained by copolymerizing a terpenewith a phenolic compound, phenol resin, modified phenol resin,xylene-phenol resin, cyclopentadiene-phenol resin, coumarone indeneresin, rosin resin, rosin ester resin, hydrogenated rosin ester resin,xylene resin, low-molecular-weight polystyrene resin, styrene copolymerresin, petroleum resins (such as C5 hydrocarbon resin, C9 hydrocarbonresin, and C5C9-hydrocarbon-copolymerized resin), hydrogenated petroleumresins, and DCPD resin. These resins may be used alone or in anycombination of two or more thereof.

The styrene copolymer resin that is a styrene block copolymer, and ahydrogenated product thereof are not particularly limited. Examplesthereof include styrene-butadiene-styrene block copolymer (SBS),styrene-isoprene-styrene block copolymer (SIS),styrene-ethylene/butylene-styrene block copolymer (SEBS),styrene-ethylene/propylene-styrene block copolymer (SEPS), andstyrene-isobutylene-styrene block copolymer (SIBS).

Of these examples, terpene-phenol resin is preferred since the resin ishighly compatible with the polymer (A) to give a high adhesive effect.When the color tone is important, hydrocarbon resin is preferred.

The use amount of the tackifier is preferably from 2 to 100 parts byweight, more preferably from 5 to 50 parts by weight, even morepreferably from 5 to 30 parts by weight for 100 parts by weight of thetotal of the polymers (A), (B), (C), (D) and (F). If the amount is lessthan 2 parts by weight, the composition does not easily gain a bondingor adhesive effect onto a substrate. If the amount is more than 100parts by weight, the composition is excessively high in viscosity to bedifficult to handle.

An epoxy-group-containing compound is usable in the composition of thepresent invention. The use of the epoxy-group-containing compound makesit possible to heighten the restorability of the cured product. Examplesof the epoxy-group-containing compound include epoxidized unsaturatedoils and fats, epoxidized unsaturated aliphatic acid esters, alicyclicepoxy compounds and epichlorohydrin derivatives; and mixtures thereof.Specific examples thereof include epoxidized soybean oil, epoxidizedlinseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate(E-PS), epoxyoctyl stearate, and epoxybutyl stearate. Of these examples,E-PS is particularly preferred. The epoxy compound is used preferably inan amount of 0.5 to 50 parts by weight for 100 parts by weight of thetotal of the polymers (A), (B), (C), (D) and (F).

An optically curable substance is usable in the composition of thepresent invention. The use of the optically curable substance makes itpossible to form a coat made from the optically curable substance ontothe surface of the cured product to solve or improve the stickiness orthe weather resistance of the cured product. The optically curablesubstance is a substance that is chemically changed in molecularstructure, in a considerably short period, by effect of light, so as tobe cured or changed in physical property. As a compound of this sort,many substances are known. Examples thereof include organic monomers,oligomers, and resins; and compositions each containing one or morethereof. Any commercially available optically curable substance isadoptable. Typical examples thereof include any unsaturated acryliccompound, any polyvinyl cinnamate, and any azidated resin.

The unsaturated acrylic compound is, for example, a monomer, anoligomer, or a mixture of the two that has one to several acrylic ormethacrylic unsaturated groups, and that is a monomer or an oligoesterwhich has a molecular weight of 10,000 or less and which is or is madefrom propylene (or butylene or ethylene) glycol di(meth)acrylate,neopentyl glycol di(meth)dimethacrylate or some other. Specific examplesthereof include especial (bifunctional)acrylates, such as productsARONIXes M-210, M-215, M-220, M-233, M-240, and M-245; (trifunctional)products ARONIXes M305, M-309, M-310, M-315, M-320, and M-325; and(polyfunctional) products ARONIX M-400. Preferred are such compoundseach having an acrylic functional group, and particularly preferred aresuch compounds each having 3 or more acrylic functional groups onaverage per molecule of the compound (the products ARONIXes are eachmanufactured by Toagosei Co., Ltd.).

Examples of the polyvinyl cinnamate include a photosensitive resinobtained by esterifying a polyvinyl alcohol with cinnamic acid to havecinnamoyl groups as photosensitive groups, and many other polyvinylcinnamate derivatives. The azidated resin is known as a photosensitiveresin having azide groups as photosensitive groups. The azidated resinis usually a photosensitive rubbery liquid into which a diazide compoundis added as a photosensitizer. Detailed examples thereof are describedin “Photosensitive Resin” (edited on Mar. 17, 1972 and published byInsatsu Gakkai Shuppanbu Ltd., p. 93 and thereafter, p. 106 andthereafter, and p. 117 and thereafter). These may be used alone or in amixture form in the state that a sensitivity intensifier is optionallyadded thereto. The addition of a ketone, a nitro compound or such asensitivity intensifier, or a promoter such as an amine may enhance theadvantageous effects.

It is advisable to use the optically curable substance in an amount of0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight for 100parts by weight of the total of the polymers (A), (B), (C), (D) and (F).If the amount is 0.1 parts or less by weight, the substance does notproduce any effect of enhancing the weather resistance. If the amount is20 parts or more by weight, the cured product tends to be excessivelyhard and be cracked.

An oxygen curable substance is usable in the composition of the presentinvention. The oxygen curable substance is, for example, an unsaturatedcompound reactive in oxygen in air, and shows an effect of reactingoxygen in air to form a cured coat in the vicinity of the surface of thecured product to prevent the stickiness of the surface or the adhesionof stain and dust onto the cured product surface, and other effects.Specific examples of the oxygen curable substance include dry oils suchas tung oil and linseed oil, and various alkyd resins each obtained bymodifying such a compound; acrylic polymers, epoxy resins, and siliconeresins each modified with a dry oil; 1,2-polybutadiene,1,4-polybutadiene, C5-C8 diene polymers, and such liquid polymers, whichare each obtained by polymerizing or copolymerizing a diene compoundsuch as butadiene, chloroprene, isoprene or 1,3-pentadiene; NBR, SBR,and such liquid copolymers, which are each obtained by copolymerizingsuch a diene compound with acrylonitrile, styrene or any other monomercopolymerizable with the diene compound to render the diene compoundmain portions of the polymer; and various modified products of theseexamples (such as maleic-acid-modified products and boiled oil modifiedproducts). These may be used alone, or in any combination of two or morethereof. Of these examples, tung oil and liquid diene polymers areparticularly preferred. The advantageous effect may be enhanced by usingthe curable composition together with a catalyst for promoting theoxidization curing reaction, or a metal drier. Examples of the catalystor the metal drier include metal salts such as cobalt naphthenate, leadnaphthenate, zirconium naphthenate, cobalt octylate, and zirconiumoctylate; and amine compounds.

The oxygen curable substance is used in an amount preferably from 0.1 to20 parts by weight, more preferably from 0.5 to 10 parts by weight for100 parts by weight of the polymers (A), (B), (C), (D) and (F). If thisuse amount is less than 0.1 parts by weight, the stain resistance is notsufficiently improved. If the amount is more than 20 parts by weight,tensile properties and others of the cured product tend to be damaged.As described in JP-A-03-160053, it is advisable to use the oxygencurable substance together with the optically curable substance.

A surface property improver may be added to the composition of thepresent invention. Examples of the surface property improver includelong-chain alkylamines such as luarylamine; phosphorous compounds suchas 2,2′-methylenebis(4,6-di-t-butylphenyl)sodium phosphate, andtris(2,4-di-t-butylpenyl) phosphate; and oxazolidine compounds.

The polymer (B) and an epoxy resin may be used together in thecomposition of the present invention. The epoxy-resin-added compositionis preferred particularly for adhesives, above all, for adhesives forexternal wall tiles. Examples of the epoxy resin include flame retardantepoxy resins such as epichlorohydrin-bisphenol A type epoxy resin,epichlorohydrin-bisphenol F type epoxy resin and glycidyl ether oftetrabromobisphenol A, novolak type epoxy resin, hydrogenated bisphenolA type epoxy resin, glycidyl ether type epoxy resin of an bisphenol Apropylene oxide adduct, p-oxybenzoic acid glycidyl ether ester typeepoxy resin, m-aminophenolic epoxy resin, diaminodiphenylmethane typeepoxy resin, urethane-modified epoxy resin, various alicyclic epoxyresins, N, N-diglycidylaniline, N,N-diglycidyl-o-toluidine, triglycidylisocyanurate, glycidyl ethers of a polyhydric alcohol, such aspolyalkylene glycol diglycidyl ether and glycerin, hydantoin type epoxyresin, and an epoxidized product of any unsaturated polymer such aspetroleum resin. However, the epoxy resin is not limited to theseresins. The epoxy resin may be an ordinarily used epoxy resin. Preferredis an epoxy resin having, in the molecule thereof, at least two epoxygroups since the resin is highly reactive when cured, and further thecured product easily forms therein a three-dimensional networkstructure. More preferred is any bisphenol A type epoxy resin or novolaktype epoxy resin.

About the use ratio between the epoxy resin and the polymer (B), theratio by weight of the polymer (B) to the epoxy resin is from 100/1 to1/100. If the ratio of the polymer (B) to the epoxy resin is less than1/100, an effect of improving the epoxy resin cured product in impactstrength or toughness is not easily obtained. If the ratio of thepolymer (B) to the epoxy resin is more than 100/1, the polymer curedproduct is insufficient in strength. A preferred value of the use ratiois not decided without reservation since the value is varied inaccordance with the usage of the curable resin composition, and otherfactors. When the epoxy resin cured product is improved in, for example,impact resistance, flexibility, toughness, peel strength and others, thecomponent (B) is used in an amount preferably from 1 to 100 parts byweight, more preferably from 5 to 100 parts by weight for 100 parts byweight of the epoxy resin. When the cured product is improved instrength, the epoxy resin is used in an amount preferably from 1 to 200parts by weight, more preferably from 5 to 100 parts by weight for 100parts by weight of the component (B).

In the case of the addition of the epoxy resin, it is natural to use acuring agent for curing the epoxy resin in the composition of thepresent invention. A usable species of the epoxy resin curing agent isnot particularly limited, and may be an ordinarily used epoxy resincuring agent. Specific examples thereof include primary and secondaryamines such as triethylenetetramine, tetraethylenepentamine,diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine,m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone,isophoronediamine, and amine-terminated polyethers; tertiary amines suchas 2,4,6-tris(dimethylaminomethyl)phenol and tripropylamine, and saltsof these tertiary amines; polyamide resins; imidazoles; dicyandiamines;trifluoroboron complex compounds; carboxylic acid anhydrides such asphthalic anhydride, hexafluorophthalic anhydride, tetrahydrophthalicanhydride, dodecinylsuccinic anhydride, pyromellitic anhydride, andchlorenic anhydride; alcohols; phenols; carboxylic acids; and diketonecomplex compounds of aluminum or zirconium. However, the epoxy resincuring agent is not limited to these compounds. These curing agents maybe used alone, or in any combination of two or more thereof.

When the epoxy resin curing agent is used, the use amount thereof rangesfrom 0.1 to 300 parts by weight for 100 parts by weight of the epoxyresin.

The epoxy resin curing agent may be a ketimine. The ketimine is stablypresent in the absence of water, and is decomposed into a primary amineand a ketone by water so that the resultant primary amine functions as aroom-temperature-curable curing agent for epoxy resin. The use of theketimine makes it possible to yield a one-pack type composition. Theketimine can be obtained by condensation reaction between an aminecompound and a carbonyl compound.

It is sufficient for the synthesis of the ketimine that a known aminecompound and carbonyl compound are used. Examples of the amine compoundinclude diamines such as ethylenediamine, propylenediamine,trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane,2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane,hexamethylenediamine, p-phenylenediamine, and p,p′-biphenylenediamine;polyhydric amines such as 1,2,3-triaminopropane, triaminobenzene,tris(2-aminoethyl)amine, and tetra(aminomethyl)methane; polyalkylenepolyamines such as diethylenetriamine, triethylenetriamine, andtetraethylenepentamine; polyoxyalkylene polyamines; and aminosilanessuch as γ-aminopropyltriethoxysilane,N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, andN-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane. Examples of thecarbonyl compound include aldehydes such as acetoaldehyde,propionaldehyde, n-butylaldehyde, isobutylaldehyde,diethylacetoaldehyde, glyoxal, and benzaldehyde; cyclic ketones such ascyclopentanone, trimethylcyclopentanone, cyclohexanone, andtrimethylcyclohexanone; and aliphatic ketones such as acetone, methylethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methylisobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone,dibutyl ketone, and diisobutyl ketone; and β-dicarbonyl compounds suchas acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethylmalonate, diethyl malonate, methyl ethyl malonate, and dibenzoylmethane.

When an imino group is present in the ketimine, the imino group may becaused to react with styrene oxide; a glycidyl ether such as butylglycidyl ether or allyl glycidyl ether; or a glycidyl ester.

The above-mentioned ketimines may be used alone or in any combination oftwo or more thereof. The ketimine is used in an amount of 1 to 100 partsby weight for 100 parts by weight of the epoxy resin. The use amount isvaried in accordance with the kind of the epoxy resin and the ketimine.

A flame retardant may be added to the composition of the presentinvention. Examples of the flame retardant includephosphorous-containing plasticizers such as polyammonium phosphate andtricresyl phosphate, aluminum hydroxide, magnesium hydroxide, andthermally expandable graphite. These flame retardants may be used aloneor in any combination of two or more thereof.

The flame retardant is used in an amount from 5 to 200 parts by weight,preferably from 10 to 100 parts by weight for 100 parts by weight of thetotal of the polymers (A), (B), (C), (D) and (F).

A foaming agent is used in the composition of the present invention,whereby the composition is usable as a foaming material. As, forexample, a spraying agent for aerosol, a liquefied gas is usable whichis butane, propane, ethane, methane, dimethyl ether or some other. Acompressed gas may be used which is made of air, oxygen, nitrogen,carbon dioxide or some other. As a hydrocarbon solvent having a boilingpoint ranging from 10 to 100° C., a spraying agent containing pentane,hexane or heptane is usable. As a foam adjustor, siloxane/oxyalkylenecopolymer is usable. The use volume of the foaming agent may be from 5to 100 mL, preferably from 5 to 50 mL, even more preferably from 5 to 20mL for 100 g of the total of the polymers (A), (B), (C), (D) and (F).

Various additives may be optionally added to the curable composition ofthe present invention to adjust various physical properties of thecurable composition or the cured product. Examples of the additivesinclude a curability adjustor, a radical inhibitor, a metal inactivatingagent, an ozone-deterioration preventer, a phosphorous-containingperoxide decomposer, a lubricant, a pigment, and an antifungal agent.These additives may be used alone or in any combination of two or morethereof. Specific examples other than the specific examples of theadditives, which have been described in the present specification, aredescribed in, for example, JP-B-04-69659, JP-B-07-108928,JP-A-63-254149, JP-A-64-22904, JP-A-2001-72854, and others.

A curable composition containing the polymer (B) of the presentinvention can be prepared in such a one-pack form that all of its blendcomponents are airtightly sealed and stored in advance and after theapplication of the composition the composition is cured by moisture inair. The composition may be prepared in such a two-pack form that acuring catalyst, a filler, a plasticizer, water and others are blendedwith each other separately as a curing preparation, and the organicpolymer composition is mixed with the blended materials before used.From the viewpoint of workability, the one-pack form is preferred.

When the curable composition is in the one-pack form, all of the blendcomponents are beforehand blended with each other; thus, when any one ofthe blend components contains water, it is preferred to dehydrate anddry the component beforehand and then use the composition, or dehydratethe component by, for example, pressure-reduction while the component isincorporated or kneaded. When the curable composition is in the two-packform, it is unnecessary to blend a silanol condensing catalyst with themain agent including the reactive-silicon-group-containing organicpolymer. Thus, even when the blend preparation contains a slight volumeof water, it is hardly feared that this blend substance is raised inviscosity or gelatinized. However, when the two-pack form curablecomposition requires storage stability over a long term, it is preferredto dehydrate and dry the composition. The method for the dehydrating anddrying is preferably a drying method by heating when the composition isin the form of a solid such as powder, and is preferably a dehydratingmethod under reduced pressure, or a dehydrating method using synthesizedzeolite, activated alumina, silica gel, caustic lime, magnesium oxide orsome other when the composition is in the form of liquid. It is alsoallowable to blend a small volume of an isocyanate compound (into thecomposition) to cause its isocyanate group to react with water, therebyattaining the dehydration. It is also allowable to blend an oxazolidinecompound such as 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine(into the composition) to cause the compound to react with water,thereby attaining the dehydration. By not only performing such adehydrating method but also adding the following (to the composition),the storage stability is further improved: a lower alcohol such asmethanol or ethanol; or an alkoxysilane compound such asn-propyltrimethoxysilane, vinyltrimethoxysilane,vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane,γ-mercaptopropylmethyldiethoxysilane, orγ-glycidoxypropyltrimethoxysilane. This manner makes a furtherimprovement in the storage stability.

The use amount of such a dehydrator, in particular, a silicon compoundreactive with water, such as vinyltrimethoxysilane, is preferably from0.1 to 20 parts by weight, more preferably from 0.5 to 10 parts byweight for 100 parts by weight of the total of the organic polymers (A),(B), (C), (D) and (F) having reactive silicon group(s).

The method for preparing the composition of the present invention is notparticularly limited, and may be an ordinary method, for example, amethod of blending the above-mentioned components with each other, andusing a mixer, a roll, a kneader or some other to knead the mixture atnormal temperature or under a mixture-heated condition, or a method ofusing an appropriate solvent in a small amount to dissolve thecomponents, and mixing the components with each other.

A composition containing the polymer (B) of the present invention is amoisture-reactive type composition, in which reaction is advanced bywater. The composition can also be used as a dual curable composition,in which the polymer-(B)-containing composition is used together with athermally curable resin, optically curable resin, or radical ray curableresin. Specifically, a curable resin is together usable which makes useof, for example, ene-thiol addition reaction, radical polymerizationreaction of (meth)acrylic groups, ring-opening polymerization reactionof epoxy groups, addition reaction through hydrosilylation, orurethanization reaction. For example, the polymer (A) of the presentinvention is curable, using ene-thiol addition reaction or additionreaction through hydrosilylation.

The composition (of any one of the aspects) of the present invention issuitable for being used as a curable composition or a sticky or adhesivecomposition, and is usable for a sticker, a sealing material forbuildings, ships, automobiles, roads and others, an adhesive, awaterproof material, a painted film waterproof material, a mold makingagent, a vibration proof material, a damping material, a soundproofmaterial, a foaming material, a paint, a spraying material, and others.A cured product obtained by curing each of the curable compositions ofthe present invention is excellent in softness and adhesiveness, andthus the product is more preferably used as a sealing material oradhesive out of the above-mentioned articles.

The composition of the present invention is usable for various articles,such as electrical/electronic part materials such as a solar batteryrear-surface sealing material, electrical/electronic parts such as aninsulating coat material for electric wires/cables, electricallyinsulating materials for devices, acoustic insulating materials, elasticadhesives, binders, contact-type adhesives, spraying-type sealingmaterials, crack repairing materials, adhesives for tiling, adhesivesfor asphalt waterproof materials, powder paints, casting materials,rubbery materials for medical care, stickers for medical care, adhesivesheets for medical care, medical machine sealing materials, dentalimpression materials, food wrapping materials, sealing materials forjoints between exterior members such as sizing boards, coatingmaterials, slip-preventing coating materials, buffer materials, primers,electromagnetic wave shielding electroconductive materials,thermoconductive materials, hot melt materials, electrical/electronicpotting agents, films, gaskets, concrete reinforcing materials,adhesives for pre-adhesion, various molding materials, antirust andwaterproof sealing materials for end surfaces (cut regions) of awire-reinforced glass piece or laminated glass piece, and liquid sealingagents used for automobile parts, parts of large vehicles such as trucksand buses, train vehicle parts, aircraft parts, ship parts, electricalmachinery parts, and various mechanical parts, and others. Whenautomobiles are given as an example, the composition is usable forvarious purposes, such as the attachment of plastic covers, trims,flanges, bumpers or windows, and the bonding and attachment of interiorparts or exterior parts. The composition is also usable as varioussealing compositions and bonding compositions since the composition canbe caused, by itself or by aid of a primer, to adhere closely to varioussubstrates, such as glass-, ceramic-material-, wood-, metal-, andresin-shaped products. The curable composition of the present inventionis usable for interior panel adhesives, exterior panel adhesives, tilingadhesives, stone-material-laying adhesives, ceiling-finishing adhesives,floor-finishing adhesives, wall-finishing adhesives,vehicle-panel-usable adhesives,electrical/electronic/precision-instrument fabricating adhesives,adhesives for bonding a leather, a fiber product, a cloth, a paperpiece, a plate and a rubber, reactive and post-crosslinkablepressure-sensitive adhesives, direct-grazing sealing materials,laminated-glass-usable sealing materials, sealing materials for an SSGconstruction method, sealing materials for working joints for buildings,and materials for civil engineering or bridges. Furthermore, thecomposition is usable as adhesive members, such as an adhesive tape andadhesive sheet.

EXAMPLES

Hereinafter, the method of the present invention will be specificallydescribed by way of working examples thereof. However, the examples donot restrict the invention.

The average number of introduced carbon-carbon unsaturated bonds into apolymer (A) in each of the examples per terminal of the polymer (A) iscalculated in accordance with the following calculation equation:

“Average number of the introduced bonds”=[(the iodine value of thepolymer (A))−(the iodine value of a precursor polymer (P) thereof)]/[thehydroxyl value of the precursor polymer (P)]

Synthesis Example 1

A polyoxypropylene glycol having a number-average molecular weight ofabout 2,000 was used as an initiator to polymerize propylene oxide inthe presence of a zinc hexacyanocobaltate glyme complex catalyst toyield a polyoxypropylene (P-1) having, at both terminals thereof,hydroxyl groups, respectively, and having a number-average molecularweight of 14,600. Subsequently, thereto was added a 28% solution ofsodium methoxide in methanol in an amount of 1.0 equivalent by molerelative to the amount of the hydroxyl groups of thishydroxyl-group-terminated polyoxypropylene (P-1). Methanol was distilledoff therefrom by vacuum devolatilization, and then allyl glycidyl etherwas added to the polymer (P-1) in an amount of 1.0 equivalent by molerelative to the amount of the hydroxyl groups of the polymer (P-1) toconduct a reaction at 130° C. for 2 hours. Thereafter, thereto was addeda solution of sodium methoxide in methanol in an amount of 0.28equivalent by mole and methanol was removed. Furthermore, thereto wasadded 3-chloro-1-propene in an amount of 1.79 equivalents by mole toconvert the hydroxyl groups at the terminals to allyl groups. Anunreacted fraction of the allyl chloride was removed by vacuumdevolatilization. Into 100 parts by weight of the resultant crudeallyl-group-terminated polyoxypropylene were incorporated 300 parts byweight of n-hexane and 300 parts by weight of water, and the mixture wasstirred. The reaction system was then centrifuged to remove water. Intothe resultant hexane solution were further incorporated 300 parts byweight of water, and the mixture was stirred. The reaction system wasagain centrifuged to remove water, and then hexane was removed by vacuumdevolatilization. The process gave a polyoxypropylene (A-1) having oneor more terminal structures (each) having 2 or more carbon-carbonunsaturated bonds and having a number-average molecular weight of about14,600. The number of introduced carbon-carbon unsaturated bonds onaverage per terminal of the polymer (A-1) was calculated. As a result,it was understood that about the polymer (A-1), the number ofcarbon-carbon unsaturated bonds introduced per terminal moiety of thepolymer was 2.0 on average.

Synthesis Example 2

A polyoxypropylene glycol having a number-average molecular weight ofabout 2,000 was used as an initiator to polymerize propylene oxide inthe presence of a zinc hexacyanocobaltate glyme complex catalyst toyield a polyoxypropylene (P-2) having, at both terminals thereof,hydroxyl groups, respectively, and having a number-average molecularweight of 28,500. Subsequently, thereto was added a 28% solution ofsodium methoxide in methanol in an amount of 1.0 equivalent by molerelative to the amount of the hydroxyl groups of thishydroxyl-group-terminated polyoxypropylene (P-2). Methanol was distilledoff therefrom by vacuum devolatilization, and then allyl glycidyl etherwas added to the polymer (P-2) in an amount of 1.0 equivalent by molerelative to the amount of the hydroxyl groups of the polymer (P-2) toconduct a reaction at 130° C. for 2 hours. Thereafter, thereto was addeda solution of sodium methoxide in methanol in an amount of 0.28equivalent by mole and methanol was removed. Furthermore, thereto wasadded 3-chloro-1-propene in an amount of 1.79 equivalents by mole toconvert the hydroxyl groups at the terminals to allyl groups.Thereafter, the same purifying operation as in Synthesis Example 1 wasmade. The process gave a polyoxypropylene (A-2) having one or moreterminal structures (each) having 2 or more carbon-carbon unsaturatedbonds and having a number-average molecular weight of about 28,500. Itwas understood that about the polymer (A-2), the number of carbon-carbonunsaturated bonds introduced per terminal moiety of the polymer was 2.0on average.

Synthesis Example 3

To the hydroxyl-group-terminated polyoxypropylene (P-2) yieldedaccording to Synthesis Example 2 was added a 28% solution of sodiummethoxide in methanol in an amount of 1.0 equivalent by mole relative tothe amount of the hydroxyl groups of the polymer (P-2). Methanol wasdistilled off therefrom by vacuum devolatilization, and then allylglycidyl ether was added to the polymer (P-2) in an amount of 2.0equivalents by mole relative to the amount of the hydroxyl groups of thepolymer (P-2) to conduct a reaction at 130° C. for 2 hours. Thereafter,thereto was added a solution of sodium methoxide in methanol in anamount of 0.28 equivalent by mole and methanol was removed. Furthermore,thereto was added 3-chloro-1-propene in an amount of 1.79 equivalents bymole to convert the hydroxyl groups at the terminals to allyl groups.Thereafter, the same purifying operation as in Synthesis Example 1 wasmade. The process gave a polyoxypropylene (A-3) having one or moreterminal structures (each) having 2 or more carbon-carbon unsaturatedbonds and having a number-average molecular weight of about 28,500. Itwas understood that about the polymer (A-3), the number of thecarbon-carbon unsaturated bonds introduced per terminal moiety of thepolymer was 3.0 on average.

Synthesis Example 4

A polyoxypropylene glycol having a number-average molecular weight ofabout 2,000 was used as an initiator to polymerize propylene oxide inthe presence of a zinc hexacyanocobaltate glyme complex catalyst toyield a polyoxypropylene (P-4) having, at both terminals thereof,hydroxyl groups, respectively, and having a number-average molecularweight of 25,500 (molecular weight in terms of that of polystyrene,measured using a system, HLC-8120 GPC, manufactured by Tosoh Corp. as aliquid sensing system, a column, TSK-GEL H type, manufactured by TosohCorp. as a column, and THF as a solvent). Subsequently, thereto wasadded a 28% solution of sodium methoxide in methanol in an amount of 1.0equivalent by mole relative to the amount of the hydroxyl groups of thishydroxyl-group-terminated polyoxypropylene (P-4). Methanol was distilledoff therefrom by vacuum devolatilization, and then allyl glycidyl etherwas added to the polymer (P-4) in an amount of 1.0 equivalent by molerelative to the amount of the hydroxyl groups of the polymer (P-4) toconduct a reaction at 130° C. for 2 hours. Thereafter, thereto was addeda solution of sodium methoxide in methanol in an amount of 0.28equivalent by mole and methanol was removed. Furthermore, thereto wasadded 3-chloro-1-propene in an amount of 1.79 equivalents by mole toconvert the hydroxyl groups at the terminals to allyl groups. Anunreacted fraction of the allyl chloride was removed by vacuumdevolatilization. Into 100 parts by weight of the resultant crudeallyl-group-terminated polyoxypropylene were incorporated 300 parts byweight of n-hexane and 300 parts by weight of water, and the mixture wasstirred. The reaction system was then centrifuged to remove water. Intothe resultant hexane solution were further incorporated 300 parts byweight of water, and the mixture was stirred. The reaction system wasagain centrifuged to remove water, and then hexane was removed by vacuumdevolatilization. The process gave a polyoxypropylene (A-4) having oneor more terminal structures (each) having 2 or more carbon-carbonunsaturated bonds and having a number-average molecular weight of about25,500. As a result, it was understood that about the polymer (A-4), thenumber of the carbon-carbon unsaturated bonds introduced per terminalmoiety of the polymer was 2.0 on average.

Synthesis Example 5

A polyoxypropylene triol having a number-average molecular weight ofabout 3,000 was used as an initiator to polymerize propylene oxide inthe presence of a zinc hexacyanocobaltate glyme complex catalyst toyield a polyoxypropylene (P-5) having, at three terminals thereof,hydroxyl groups, respectively, and having a number-average molecularweight of 26,200. Subsequently, thereto was added a 28% solution ofsodium methoxide in methanol in an amount of 1.0 equivalent by molerelative to the amount of the hydroxyl groups of thishydroxyl-group-terminated polyoxypropylene (P-5). Methanol was distilledoff therefrom by vacuum devolatilization, and then allyl glycidyl etherwas added to the polymer (P-5) in an amount of 1.0 equivalent by molerelative to the amount of the hydroxyl groups of the polymer (P-5) toconduct a reaction at 130° C. for 2 hours. Thereafter, thereto was addeda solution of sodium methoxide in methanol in an amount of 0.28equivalent by mole and methanol was removed. Furthermore, thereto wasadded 3-chloro-1-propene in an amount of 1.79 equivalents by mole toconvert the hydroxyl groups at the terminals to allyl groups.Thereafter, the same purifying operation as in Synthesis Example 1 wasmade. The process gave a polyoxypropylene (A-5) having one or moreterminal structures (each) having 2 or more carbon-carbon unsaturatedbonds and having a number-average molecular weight of about 26,200. Itwas understood that about the polymer (A-5), the number of thecarbon-carbon unsaturated bonds introduced per terminal moiety of thepolymer was 2.0 on average.

Synthesis Experimental Example 6

Butanol was used as an initiator to polymerize propylene oxide in thepresence of a zinc hexacyanocobaltate glyme complex catalyst to yield apolyoxypropylene (P-6) having, at one of both terminals thereof,hydroxyl groups, and having a number-average molecular weight of 4900.Subsequently, thereto was added a 28% solution of sodium methoxide inmethanol in an amount of 1.0 equivalent by mole relative to the amountof the hydroxyl groups of this hydroxyl-group-terminatedpolyoxypropylene (P-6). Methanol was distilled off therefrom by vacuumdevolatilization, and then allyl glycidyl ether was added to the polymer(P-6) in an amount of 1.0 equivalent by mole relative to the amount ofthe hydroxyl groups of the polymer (P-6) to conduct a reaction at 130°C. for 2 hours. Thereafter, thereto was added a solution of sodiummethoxide in methanol in an amount of 0.28 equivalent by mole andmethanol was removed. Furthermore, thereto was added 3-chloro-1-propenein an amount of 1.79 equivalents by mole to convert the hydroxyl groupsat the terminals to allyl groups. Thereafter, the same purifyingoperation as in Synthesis Example 1 was made. The process gave apolyoxypropylene (A-6) having one or more terminal structures (each)having 2 or more carbon-carbon unsaturated bonds and having anumber-average molecular weight of about 4,900. It was understood thatabout the polymer (A-6), one of both the terminals was a butyloxy group,and the number of the carbon-carbon unsaturated bonds introduced intothe other of the terminal moieties was 2.0 on average.

Synthesis Comparative Example 1

To the hydroxyl-group-terminated polyoxypropylene (P-1) yieldedaccording to Synthesis Example 1 was added a 28% solution of sodiummethoxide in methanol in an amount of 1.2 equivalents relative to theamount of the hydroxyl groups of the polymer (P-1). Methanol wasdistilled off therefrom by vacuum devolatilization, and then thereto wasadded 3-chloro-1-propene in an amount of 2.0 equivalents by molerelative to the amount of the hydroxyl groups of the polymer (P-1) toconvert the hydroxyl groups at the terminals to allyl groups.Thereafter, the same purifying operation as in Synthesis Example 1 wasmade. The process gave a polyoxypropylene (P-1′) having, at a or eachterminal thereof, one carbon-carbon unsaturated bond and having anumber-average molecular weight of about 14,600. It was understood thatabout the polymer (P-1′), the number of the carbon-carbon unsaturatedbond(s) introduced per terminal moiety of the polymer was 1.0 onaverage.

Synthesis Comparative Example 2

To the hydroxyl-group-terminated polyoxypropylene (P-2) yieldedaccording to Synthesis Example 2 was added a 28% solution of sodiummethoxide in methanol in an amount of 1.2 equivalents relative to theamount of the hydroxyl groups of the polymer (P-2). Methanol wasdistilled off therefrom by vacuum devolatilization, and then thereto wasadded 3-chloro-1-propene in an amount of 2.0 equivalents by molerelative to the amount of the hydroxyl groups of the polymer (P-2) toconvert the hydroxyl groups at the terminals to allyl groups.Thereafter, the same purifying operation as in Synthesis Example 1 wasmade. The process gave a polyoxypropylene (P-2′) having, at a or eachterminal thereof, one carbon-carbon unsaturated bond and having anumber-average molecular weight of about 28,500. It was understood thatabout the polymer (P-2′), the number of the carbon-carbon unsaturatedbond(s) introduced per terminal moiety of the polymer was 1.0 onaverage.

Synthesis Comparative Example 3

To the hydroxyl-group-terminated polyoxypropylene (P-4) yieldedaccording to Synthesis Example 4 was added a 28% solution of sodiummethoxide in methanol in an amount of 1.2 equivalents relative to theamount of the hydroxyl groups of the polymer (P-4). Methanol wasdistilled off therefrom by vacuum devolatilization, and then thereto wasadded 3-chloro-1-propene in an amount of 2.0 equivalents by molerelative to the amount of the hydroxyl groups of the polymer (P-4) toconvert the hydroxyl groups at the terminals to allyl groups.Thereafter, the same purifying operation as in Synthesis Example 1 wasmade. The process gave a polyoxypropylene (P-4′) having, at a or eachterminal thereof, one carbon-carbon unsaturated bond and having anumber-average molecular weight of about 25,500. It was understood thatabout the polymer (P-4′), the number of the carbon-carbon unsaturatedbond(s) introduced per terminal moiety of the polymer was 1.0 onaverage.

Synthesis Comparative Example 4

To the hydroxyl-group-terminated polyoxypropylene (P-5) yieldedaccording to Synthesis Example 5 was added a 28% solution of sodiummethoxide in methanol in an amount of 1.2 equivalents relative to theamount of the hydroxyl groups of the polymer (P-5). Methanol wasdistilled off therefrom by vacuum devolatilization, and then thereto wasadded 3-chloro-1-propene in an amount of 2.0 equivalents by molerelative to the amount of the hydroxyl groups of the polymer (P-5) toconvert the hydroxyl groups at the terminals to allyl groups.Thereafter, the same purifying operation as in Synthesis Example 1 wasmade. The process gave a polyoxypropylene (P-5′) having, at a or eachterminal thereof, one carbon-carbon unsaturated bond and having anumber-average molecular weight of about 26,200. It was understood thatabout the polymer (P-5′), the number of the carbon-carbon unsaturatedbond(s) per terminal moiety of the polymer was 1.0 on average.

Synthesis Comparative Example 5

To the hydroxyl-group-terminated polyoxypropylene (P-6) yieldedaccording to Synthesis Example 6 was added a 28% solution of sodiummethoxide in methanol in an amount of 1.2 equivalents relative to theamount of the hydroxyl groups of the polymer (P-6). Methanol wasdistilled off therefrom by vacuum devolatilization, and then thereto wasadded 3-chloro-1-propene in an amount of 2.0 equivalents by molerelative to the amount of the hydroxyl groups of the polymer (P-6) toconvert the hydroxyl groups at the terminals to allyl groups.Thereafter, the same purifying operation as in Synthesis Example 1 wasmade. The process gave a polyoxypropylene (P-6′) having, at a or eachterminal thereof, one carbon-carbon unsaturated bond. It was understoodthat about the polymer (P-6′), one of both the terminals was a butyloxygroup, and the number of the carbon-carbon unsaturated bond(s)introduced into the other of the terminal moieties was 1.0 on average.

Synthesis Example 7

To 500 g of the polymer (A-1) yielded according to Synthesis Example 1,which had two carbon-carbon unsaturated bonds on average per terminalmoiety of the polymer, was added 50 μL of a platinum divinyldisiloxanecomplex solution (a solution of platinum in 2-propanol which had aplatinum-converted concentration of 3% by weight). While this system wasstirred, 18.2 g of dimethoxymethylsilane was dropwise and slowly addedthereto. The resultant mixed solution was caused to undergo a reactionat 90° C. for 2 hours, and then an unreacted fraction ofdimethoxymethylsilane was distilled off under a reduced pressure toyield a reactive-silicon-group-containing polyoxypropylene (B-1) havinga number-average molecular weight of about 14,600 and having one or moreterminal structures (each) having two or more dimethoxymethylsilylgroups. It was understood that the polymer (B-1) haddimethoxymethylsilyl groups that were 1.6 in number on average perterminal of the polymer, and had dimethoxymethylsilyl groups that were3.2 in number on average per molecule of the polymer.

Synthesis Example 8

To 500 g of the polyoxypropylene (A-2) yielded according to SynthesisExample 2, which had two carbon-carbon unsaturated bonds on average perterminal moiety of the polymer, was added 50 μL of a platinumdivinyldisiloxane complex solution. While this system was stirred, 9.6 gof dimethoxymethylsilane was dropwise and slowly added thereto. Theresultant mixed solution was caused to undergo a reaction at 90° C. for2 hours, and then an unreacted fraction of dimethoxymethylsilane wasdistilled off under a reduced pressure to yield a polyoxypropylene (B-2)having a number-average molecular weight of about 28,500 and having oneor more terminal structures (each) having two or moredimethoxymethylsilyl groups. It was understood that the polymer (B-2)had dimethoxymethylsilyl groups that were 1.7 in number on average perterminal of the polymer, and had dimethoxymethylsilyl groups that were3.4 in number on average per molecule of the polymer.

Synthesis Example 9

To 500 g of the polyoxypropylene (A-2), which had two carbon-carbonunsaturated bonds on average per terminal moiety of the polymer, wasadded 50 μL of a platinum divinyldisiloxane complex solution. While thissystem was stirred, 14.7 g of triethoxysilane was dropwise and slowlyadded thereto. The resultant mixed solution was caused to undergo areaction at 90° C. for 2 hours, and then an unreacted fraction oftriethoxysilane was distilled off under a reduced pressure to yield apolyoxypropylene (B-3) having a number-average molecular weight of about28,500 and having one or more terminal structures (each) having two ormore triethoxysilyl groups. It was understood that the polymer (B-3) hadtriethoxysilyl groups that were 1.7 in number on average per terminal ofthe polymer, and had triethoxysilyl groups that were 3.4 in number onaverage per molecule of the polymer.

Synthesis Comparative Example 6

To 500 g of the polymer (P-1′) yielded in Synthesis Comparative Example1 was added 50 μL of a platinum divinyldisiloxane complex solution.While this system was stirred, 8.9 g of dimethoxymethylsilane wasdropwise and slowly added thereto. The resultant mixed solution wascaused to undergo a reaction at 90° C. for 2 hours, and then anunreacted fraction of dimethoxymethylsilane was distilled off under areduced pressure to yield a reactive-silicon-group-containingpolyoxypropylene (S-1) having a number-average molecular weight of about14,600 and having a or each terminal moiety having onedimethoxymethylsilyl group. It was understood that the polymer (S-1) hada dimethoxymethylsilyl group that was 0.75 in number on average perterminal of the polymer, and had dimethoxymethylsilyl groups that were1.5 in number on average per molecule of the polymer.

Synthesis Comparative Example 7

To 500 g of the polymer (P-2′) yielded in Synthesis Comparative Example2 was added 50 μL of a platinum divinyldisiloxane complex solution.While this system was stirred, 4.8 g of dimethoxymethylsilane wasdropwise and slowly added thereto. The resultant mixed solution wascaused to undergo a reaction at 90° C. for 2 hours, and then anunreacted fraction of dimethoxymethylsilane was distilled off under areduced pressure to yield a polyoxypropylene (S-2) having anumber-average molecular weight of about 28,500 and having a or eachterminal moiety having one dimethoxymethylsilyl group. It was understoodthat the polymer (S-2) had a dimethoxymethylsilyl group that was 0.8 innumber on average per terminal of the polymer, and haddimethoxymethylsilyl groups that were 1.6 in number on average permolecule of the polymer.

Synthesis Comparative Example 8

To 500 g of the polymer (P-2′) yielded in Synthesis Comparative Example2 was added 50 μL of a platinum divinyldisiloxane complex solution.While this system was stirred, 7.4 g of triethoxysilane was dropwise andslowly added thereto. The resultant mixed solution was caused to undergoa reaction at 90° C. for 2 hours, and then an unreacted fraction oftriethoxysilane was distilled off under a reduced pressure to yield apolyoxypropylene (S-3) having a number-average molecular weight of about28,500 and having a or each terminal moiety having one triethoxysilylgroup. It was understood that the polymer (S-3) had a triethoxysilylgroup that was 0.8 in number on average per terminal of the polymer, andhad triethoxysilyl groups that were 1.6 in number on average permolecule of the polymer.

Examples 1, 2 and 3, and Comparative Examples 1, 2 and 3

Into 100 parts by weight of a polymer shown in Table 1 (in each of theseexamples) were incorporated diisodecyl phthalate (manufactured by KyowaHakko Kogyo Co., Ltd., and referred to as DIDP hereinafter), 160 partsby weight of precipitated calcium carbonate (NEOLIGHT SP, manufacturedby Takehara Kagaku Kogyo Co., Ltd.), 54 parts by weight of heavy calciumcarbonate (WHITON SB, manufactured by Shiraishi Calcium Kaisha, Ltd.),20 parts by weight of titanium oxide (TIPAQUE R820, manufactured byIshihara Sangyo Kaisha, Ltd.), 2 parts by weight of an amide wax(CLAVERACK SL, manufactured by a company, Cleverley), 1 part by weightof 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole (TINUVIN327, manufactured by BASF Corp.), and 1 part by weight ofbis(2,2,6,6-tetramethyl-4-pyperidyl) sebacate (SANOL LS770, manufacturedby Ciba Specialty Chemicals Ltd.). A three-roll machine was used todisperse these components into an even state. Thereafter, thereto wereadded 3 parts by weight of vinyltrimethoxysilane (A-171, manufactured byDow Corning Toray Co., Ltd.), 3 parts by weight of[3-(2-aminoethyl)aminopropyl]trimethoxysilane (KBM 603, manufactured byShin-Etsu Chemical Co., Ltd.), and 2 parts by weight of dibutyltinbisacetyleacetonate (U-220H, manufactured by Nitto Kasei Co., Ltd.), andall the components were sufficiently mixed with each other with aspatula. An autorotation/orbital-revolution mixer was then used to mixthe components with each other into an even state, and defoam themixture. The composition was filled into a mold frame, and cured at 23°C. and 50% RH for 3 days, and further cured at 50° C. for 4 days toproduce a sheet-form cured product having a thickness of about 3 mm. Thesheet-form cured product was punched out into #3-dumbbell-form samples.One of the samples was subjected to a tensile strength test at 23° C.and 50% RH to measure the stress at 50% elongation, and the strength atbreaking. The tensile strength was measured at a tensile rate of 200mm/min., using an autograph (AGS-J) manufactured by Shimadzu Corp.Marked lines were drawn onto a necking region of another of thedumbbell-form cured products at intervals of 20 mm. The product wasfixed in the state of being stretched to set each of the intervalsbetween the marked lines to 40 mm, and then allowed to stand still at23° C. and 50% RH for 24 hours. The fixation was then cancelled. Afterone hour, one day and one week from the cancellation, the respectiverecoveries were measured. The recoveries were each calculated inaccordance with the following equation: the recovery (%)=(40−thedistance (mm) between any two of the marked lines)/20. The results areshown in Table 1.

TABLE 1 Com- Com- Example Example Example parative parative 1 2 3Example 1 Example 2 Polymer B-1 B-2 B-3 S-1 S-2 Re- After B B A D D cov-one ery hour After A A A C D one day After A A A B D seven days

As shown in Table 1, the respective compositions containing the polymers(B-1), (B-2), and (B-3) corresponding to the polymer (B) of the presentinvention each gave a cured product higher in hardness, strength andrecovery than the respective compositions containing the polymers (S-1),(S-2) and (S-3), which were equal to the polymers (B-1) to (B-3) in mainchain structure, molecular weight, and silicon group structure,respectively, but different therefrom in the number or quantity of theterminated silicon groups introduced.

Synthesis Example 10

To 500 g of the polymer (A-4) yielded according to Synthesis Example 4was added 50 μL of a solution of a platinum divinyldisiloxane complex.While the reaction system was stirred, thereto was dropwise and slowlyadded 11.2 g of trimethoxysilane. The mixed solution was caused toundergo a reaction at 90° C. for 2 hours, and then an unreacted fractionof trimethoxysilane was distilled off under a reduced pressure to yielda reactive-silicon-group-containing polyoxypropylene (B-4) having anumber-average molecular weight of about 25,500 and having one or moreterminal structures (each) having two or more trimethoxysilyl groups. Itwas understood that the polymer (B-4) had dimethoxymethylsilyl groupsthat were 1.6 in number on average per terminal of the polymer, and haddimethoxymethylsilyl groups that were 3.2 in number on average permolecule of the polymer.

Synthesis Example 11

Over 4 hours, to 200 g of isobutyl alcohol (IBA) heated to 105° C. wasdropwise added a solution obtained by dissolving 11.5 g ofazobis-2-methylbutyronitrile as a polymerization initiator into amixture composed of 300 g of methyl methacrylate, 115 g of 2-ethylhexylacrylate, 46 g of γ-methacryloxypropyltrimethoxysilane, 37 g ofγ-mercaptopropyltrimethoxysilane, and 140 g of IBA. Thereafter, thepolymerizable components therein were polymerized to yield a(meth)acrylate copolymer (C-1) having a solid concentration of 60% and anumber-average molecular weight of 2,200, and having trimethoxysilylgroups which were 1.5 in number on average per molecule of the polymer.

Synthesis Example 12

The methacrylate copolymer (C-1) solution yielded according to SynthesisExample 11 was mixed with 60 parts of thereactive-silicon-group-containing polyoxypropylene (B-4) into an evenstate to adjust the polymer (C-1) solid content in the solution into 40parts. Therefrom, isobutyl alcohol was distilled off through a rotaryevaporator to yield a polymer mixture (BC-4).

Synthesis Comparative Example 9

To 500 g of the polymer (P-2′) yielded in Synthesis Comparative Example2 was added 50 μL of a solution of a platinum divinyldisiloxane complex.While the reaction system was stirred, thereto was dropwise and slowlyadded 5.5 g of trimethoxysilane. The mixed solution was caused toundergo a reaction at 90° C. for 2 hours, and then an unreacted fractionof trimethoxysilane was distilled off under a reduced pressure to yielda reactive-silicon-group-containing polyoxypropylene (S-4) having anumber-average molecular weight of about 28,500 and having, at a or eachterminal, one trimethoxysilyl group. It was understood that the polymer(S-4) had a trimethoxysilyl group that was 0.8 in number on average perterminal of the polymer, and had trimethoxysilyl groups that were 1.6 innumber on average per molecule of the polymer.

Synthesis Comparative Example 10

The methacrylate copolymer (C-1) solution yielded according to SynthesisExample 11 was mixed with 60 parts of thereactive-silyl-group-containing polyoxypropylene (S-4) into an evenstate to adjust the polymer (C-1) solid content in the solution into 40parts. Therefrom, isobutyl alcohol was distilled off through a rotaryevaporator to yield a polymer mixture (SC-4).

Example 4 and Comparative Example 4

Into 100 parts by weight of each of the polymer (BC-4) and the polymer(SC-4) were incorporated 3.0 parts by weight of tin octylate, 0.5 partby weight of laurylamine, and 0.6 part by weight of water into an evenstate while the polymer was stirred. The resultant was centrifuged to bedefoamed. The resultant mixture was filled into a mold frame made ofpolyethylene not to put air bubbles into the frame. The mixture wascured at 23° C. and 50% RH for 1 hour and further cured at 70° C. for 20hours to produce a sheet having a thickness of about 3 mm. The sheet waspunched out into #3-dumbbell-form samples. One of the samples wassubjected to a tensile strength test at 23° C. and 50% RH to measure thestress at 50% elongation (M50), the strength at breaking (TB), and theelongation at breaking (EB). The tensile strength was measured at atensile rate of 200 mm/min., using an autograph (AGS-J) manufactured byShimadzu Corp. The results are shown in Table 2.

TABLE 2 Comparative Example 4 Example 4 Polymer BC-4 SC-4 Cured productM50 (MPa) 0.8 0.9 physical TB (MPa) 8.6 4.9 properties EB (%) 120 110

It is understood that when the polymer (B-4) having one or more terminalstructures (each) having two or more reactive silicon groups is comparedwith the polymer (S-4) having, at a or each terminal, one reactivesilicon group, the strength of the cured product made of the polymer(C-1) combined with the mixture (BC-4) is drastically high.

Synthesis Example 13

To 500 g of the polyoxypropylene (A-3) yielded according to SynthesisExample 3, which had ally groups that were 3 in number on average perterminal of the polymer, was added 50 μL of a solution of a platinumdivinyldisiloxane complex. While the reaction system was stirred,thereto was dropwise and slowly added 12.8 g of dimethoxymethylsilane.The mixed solution was caused to undergo a reaction at 90° C. for 2hours, and then an unreacted fraction of dimethoxymethylsilane wasdistilled off under a reduced pressure to yield a polyoxypropylene (B-5)having a number-average molecular weight of about 28,500 and having oneor more terminal structures (each) having two or moredimethoxymethylsilyl groups. It was understood that the polymer (B-5)had dimethoxymethylsilyl groups that were 2.4 in number on average perterminal of the polymer, and had dimethoxymethylsilyl groups that were4.8 in number on average per molecule of the polymer.

Synthesis Example 14

The same operations as in Synthesis Example 13 were made except that12.8 g of dimethoxymethylsilane was changed to 14.7 g oftrimethoxysilane, so as to yield a polyoxypropylene (B-6) having one ormore terminal structures (each) having two or more reactive silicongroups. It was understood that the polymer B-6 had dimethoxymethylsilylgroups that were 2.4 in number on average per terminal of the polymer,and had dimethoxymethylsilyl groups that were 4.8 in number on averageper molecule of the polymer.

Synthesis Example 15

The same operations as in Synthesis Example 13 were made except that12.8 g of dimethoxymethylsilane was changed to 6.4 g ofdimethoxymethylsilane and 7.4 g of trimethoxysilane, so as to yield apolyoxypropylene (B-7) having a number-average molecular weight of about28,500 and having one or more terminal structures (each) having two ormore reactive silicon groups. It was understood that the polymer (B-7)had dimethoxymethylsilyl groups and trimethoxysilyl groups that were 1.2and 1.2, respectively, in number on average per terminal of the polymer,and had the reactive silicon groups that were 4.8 in number on averageper molecule of the polymer.

Synthesis Example 16

The same operations as in Synthesis Example 12 were made except that thepolymer (B-4) was changed to the polymer (B-5), so as to yield a polymermixture (BC-5).

Synthesis Example 17

The same operations as in Synthesis Example 12 were made except that thepolymer (B-4) was changed to the polymer (B-6), so as to yield a polymermixture (BC-6).

Synthesis Example 18

The same operations as in Synthesis Example 12 were made except that thepolymer (B-4) was changed to the polymer (B-7), so as to yield a polymermixture (BC-7).

Synthesis Comparative Example 11

The same operations as in Synthesis Comparative Example 10 were madeexcept that the polymer (S-4) was changed to the polymer (S-2), so as toyield a polymer mixture (SC-2).

Examples 5 and 6 and Comparative Example 5

Using the polymer or a combination of the polymers in Table 3 (in eachof the examples), a cured product was produced in the same way as inExample 1. Tensile properties thereof were evaluated. The results areshown in Table 3.

TABLE 3 Polymer Comparative (composition ratio) Example 5 Example 6Example 5 BC-5 50 BC-6 50 BC-7 100 SC-2 50 SC-4 50 M50 MPa 1.6 1.3 1.0M100 MPa 11.1 11.0 — TB MPa 11.8 11.0 5.2 EB % 100 100 95

The respective polymers contained in the curable compositions of theworking examples are each a polymer mixture of a polyoxyalkylenecontaining reactive silicon groups that are two in number on average perterminal of the polymer, and containing, as the reactive silicon groups,both of trimethoxysilyl and dimethoxymethylsilyl groups, and areactive-silicon-group-containing (meth)acrylate copolymer (C). It isunderstood that the polymers give respective cured products higher inhardness and strength than the polymers of the corresponding comparativeexamples.

Synthesis Comparative Example 12

To the hydroxyl-group-terminated polyoxypropylene (P-6) yieldedaccording to Synthesis Example 6 was added a 28% solution of sodiummethoxide in methanol in an amount of 1.2 equivalents by mole relativeto the amount of the hydroxyl groups of the polymer (P-6). Methanol wasdistilled off therefrom by vacuum devolatilization, and then thereto wasadded 3-chloro-1-propene in an amount of 2.0 equivalents by molerelative to the amount of the hydroxyl groups of the polymer (P-6) toconvert the hydroxyl groups at the terminals to allyl groups.Thereafter, the same purifying operation as in Synthesis Example 1 wasmade. The process gave a polyoxypropylene polymer having, at one of bothterminals thereof, an allyl group. To 500 g of this polymer was added 50μL of a solution of a platinum divinyldisiloxane complex. While thereaction system was stirred, thereto was dropwise and slowly added 35.3g of dimethoxymethylsilane. The mixed solution was caused to undergo areaction at 90° C. for 2 hours, and then an unreacted fraction ofdimethoxymethylsilane was distilled off under a reduced pressure toyield a polyoxypropylene (D−1) having, at a or each terminal thereof,one dimethoxymethylsilyl group. It was understood that the polymer (D−1)had a dimethoxymethylsilyl group that was 0.8 in number on average permolecule of the polymer.

Examples 7 to 9

Into 100 parts by weight of a polymer or a combination of polymers shownin Table 4 (in each of examples) were incorporated 65 parts by weight ofpolypropylene glycol (ACTCOL 21-56, manufactured by Mitsui Chemicals,Inc.), 30 parts by weight of precipitated calcium carbonate (HAKUENKACCR, manufactured by Shiraishi Calcium Kaisha, Ltd.), and 70 parts byweight of the carbonate (WHITON SB). A three-roll machine was used todisperse these components into an even state. However, in Example 9, 80parts by weight of the polymer (B-1) and 20 parts by weight of theplasticizer DIDP were combined with each other into 100 parts by weight.Thereafter, thereto were added 3 parts by weight of the product A-171, 4parts by weight of that KBM 603, and 1 part by weight of that U-220H,and all the components were sufficiently mixed with each other with aspatula. An autorotation/orbital-revolution mixer was then used to mixthe components with each other into an even state, and defoam themixture. The resultant composition was filled into a mold frame, andcured at 23° C. and 50% RH for 3 days, and further cured at 50° C. for 4days to produce a sheet-form cured product having a thickness of about 3mm. In the same way as in Example 1, the cured product was measuredabout the modulus at 50% elongation, and the strength at breaking.Moreover, an evaluating fraction of the composition was filled into amold frame having a thickness of about 5 mm, using a spatula. The timewhen the surface thereof had been adjusted into a flat form was definedas the curing start time (of the composition). The surface was touchedwith a spatula. The time when the composition had come not to adhereonto the spatula was defined as the skinning time. Thus, the period forthe curing was measured. Just after the mixing in the mixer, a BM typeviscometer (using a rotor No. 4) was used to measure the viscosity ofthe composition. The results are shown in Table 4.

TABLE 4 Polymer (composition ratio) Example 7 Example 8 Example 9 B-1 80100 80 D-1 20 DIDP (plasticizer) 20 Viscosity Pa-s/2 rpm 22 31 24Skinning min 55 40 60 period Cured M50 (MPa) 0.3 0.5 0.3 product TB(MPa) 1.1 1.0 0.9 physical EB (%) 220 110 160 properties

It is understood that the use of the polymers (B-1) and (D-1) togethermakes it possible to make the curable composition lower in viscosity andmake the resultant cured product higher in elongation without loweringthe breaking strength thereof than the use of the polymer (B-1) alone.

Synthesis Example 19

To 500 g of the polymer (A-2) yielded according to Synthesis Example 2were added 10 g of trimethyl orthoacetate and 50 μL of a solution of aplatinum divinyldisiloxane complex. While the reaction system wasstirred, thereto was dropwise and slowly added 10.3 g oftrimethoxysilane. The mixed solution was caused to undergo a reaction at90° C. for 2 hours, and then an unreacted fraction of trimethoxysilanewas distilled off under a reduced pressure to yield a polyoxypropylene(B-8) having a number-average molecular weight of about 28,500 andhaving one or more terminal structures (each) having two or moretrimethoxysilyl groups. It was understood that the polymer (B-8) hadtrimethoxysilyl groups that were 1.6 in number on average per terminalof the polymer, and had trimethoxysilyl groups that were 3.2 in numberon average per molecule of the polymer.

Synthesis Example 20

The same operations as in Synthesis Example 12 were made except that thepolymer (B-4) was changed to the polymer (B-8), so as to yield a polymermixture (BC-8).

Synthesis Comparative Example 13

To 500 g of the polymer (P-5′) yielded in Synthesis Comparative Example4 was added 50 μL of a platinum divinyldisiloxane complex solution.While this system was stirred, 6.3 g of trimethoxysilane was dropwiseand slowly added thereto. The resultant mixed solution was caused toundergo a reaction at 90° C. for 2 hours, and then an unreacted fractionof trimethoxysilane was distilled off under a reduced pressure to yielda polyoxypropylene (S-5) having a number-average molecular weight ofabout 26,200 and having, at a or each terminal thereof, onetrimethoxysilyl group. It was understood that the polymer (S-5) had atrimethoxysilyl group that was 0.7 in number on average per terminal ofthe polymer, and had trimethoxysilyl groups that were 2.0 in number onaverage per molecule of the polymer.

Synthesis Comparative Example 14

The same operations as in Synthesis Comparative Example 10 were madeexcept that the polymer (S-4) was changed to the polymer (S-5), so as toyield a polymer mixture (SC-5).

Examples 10 and 11 and Comparative Examples 6 and 7

In accordance with a composition as shown in Table 5 (in each of theseexamples), 100 parts by weight of the polymer (B-2), (BC-8), (S-2) or(SC-5) were mixed with 10 or 20 parts by weight of a DT resin, i.e., amethylsilicone oligomer having, in a single molecule thereof, 14% byweight of silicon-atom-bonded methoxy groups (XR31-B2733, manufacturedby Momentive Performance Materials Japan LLC), and 1 part by weight ofdibutyltin bisacetylacetonate. The mixture was centrifuged to bedefoamed, and then filled into a mold frame made of polyethylene not toput air bubbles into the frame. The mixture was cured at 23° C. and 50%RH for 3 days and further cured at 50° C. for 4 days to produce asheet-form cured product having a thickness of 3 mm. The sheet waspunched out into #3-dumbbell-form samples. In the same way as in Example1, the samples were measured about the stress at 50% elongation (M50),the stress at 100% elongation (M100), and the strength at breaking (TB)and the elongation at breaking (EB) thereof. The results are shown inTable 5.

TABLE 5 Polymer (composition Example Example Comparative Comparativeratio) 10 11 Example 6 Example 7 B-2 100 BC-8 100 S-2 100 SC-5 100XR31-B2733 10 20 10 20 M50 (MPa) 0.5 3.1 0.3 2.0 M100 (MPa) 0.7 — 0.4 —TB (MPa) 0.8 10.8 0.7 4.9 EB (%) 130 90 220 80

It is understood that a combination of a curable composition containingthe polymer (B) of the present invention with a methylsilicone makes itpossible to yield a cured product having a higher breaking strength thana curable composition containing the polymer (S-2) or the polymermixture (SC-5) of the corresponding comparative example.

Synthesis Comparative Example 15

To the hydroxyl-group-terminated polyoxyalkylene (P-2) yielded inSynthesis Example 2 was added a 28% solution of sodium methoxide inmethanol in an amount of 1.2 equivalents by mole relative to the amountof the hydroxyl groups of this polymer (P-2). Methanol was distilled offtherefrom by vacuum devolatilization, and then to the polymer was added3-chloro-2-methyl-1-propene in an amount of 1.5 equivalents by molerelative to the amount of the hydroxyl groups of the polymer (P-2) toconvert the hydroxyl groups at the terminals to methallyl groups. Anunreacted fraction of 3-chloro-2-methyl-1-propene was removed byreduced-pressure devolatilization. Into 100 parts by weight of theresultant crude methallyl-group-terminated polyoxypropylene wereincorporated 300 parts by weight of n-hexane and 300 parts by weight ofwater, and the mixture was stirred. The reaction system was thencentrifuged to remove water. Into the resultant hexane solution werefurther incorporated 300 parts by weight of water, and the mixture wasstirred. The reaction system was again centrifuged to remove water, andthen hexane was removed by reduced-pressure devolatilization. Theprocess gave a polyoxypropylene polymer (P-7) having, at a or eachterminal moiety, a methallyl group. To 500 g of this polymer (P-7) wasadded 150 μL of a platinum divinyldisiloxane complex solution. Whilethis system was stirred, 12.0 g of dimethoxymethylsilane was dropwiseand slowly added thereto. This mixed solution was caused to undergo areaction at 100° C. under a 6%-oxygen condition for 6 hours, and then anunreacted fraction of dimethoxymethylsilane was distilled off under areduced pressure to yield a polyoxypropylene (S-6) having anumber-average molecular weight of about 28,500 and having, at a or eachterminal thereof, one dimethoxymethylsilyl group. It was understood thatthe polymer (S-6) had a dimethoxymethylsilyl group that was 1.0 innumber on average per terminal of the polymer, and haddimethoxymethylsilyl groups that were 2.0 in number on average permolecule of the polymer.

Examples 12 to 14, and Comparative Examples 8 to 12

Into 100 parts by weight of a reactive-silicon-group-containing polymershown in Table 6 (in each of these examples) were incorporated 55 partsby weight of DIDP, 120 parts by weight of the carbonate CCR, 20 parts byweight of the product TIPAQUE R820, 2 parts by weight of an aliphaticacid amide wax (DISPARLON 6500, manufactured by Kusumoto Chemicals,Ltd.), 1 part by weight of the product TINUVIN 327, and 1 part by weightof the product SANOL LS770. A three-paint-roll machine was used todisperse these components into an even state. Thereafter, thereto wereadded 2 parts by weight of the product A-171, 3 to 7 parts by weight ofthat KBM 603, and 2 parts by weight of that NEOSTANNU-220H, and all thecomponents were sufficiently mixed with each other. Anautorotation/orbital-revolution mixer was then used to mix thecomponents with each other into an even state, and defoam the mixture.The resultant composition was filled into a mold frame having athickness of about 5 mm, using a spatula. The time when the surfacethereof had been adjusted into a flat form was defined as the curingstart time, and the period for curing the surface was measured. Thesurface was touched with a spatula at intervals of 1 minute until 10minutes elapsed from the start, at intervals of 5 minutes until 60minutes elapsed therefrom, and at intervals of 10 minutes thereafter.The time when the composition had come not to adhere onto the spatulawas defined as the skinning time. Thus, the period for the curing wasmeasured. Furthermore, the composition was painted into the form ofbeads onto each of an aluminum substrate and a soft polyvinyl chloridesubstrate. The resultant was cured at 23° C. and 50% RH in a thermostatfor 7 days. The resultant bonding-test piece was used to check the stateof the bonded surface when the bonded surface was broken in a 90-degreehand peel test. The proportion of cohesive failure is represented by C;and that of interfacial peeling, by A. The results are shown in Table 6.In Table 6 are shown the species of the polymer, and the proportion ofthe product KBM 603. The other components are common between the presentexamples.

TABLE 6 Example Example Example Comparative Comparative ComparativeComparative Comparative 12 13 14 Example 8 Example 9 Example 10 Example11 Example 12 Polymer B-2 B-2 B-2 S-2 S-2 S-6 S-6 S-6 KBM 603 3 5 7 3 53 5 7 (parts by weight) Skinning min. 55 45 35 45 35 80 70 55 periodAdhesiveness Aluminum C100 C100 C100 C100 C100 C100 C100 C100 plate 90°Hand peel Soft A100 C100 C100 A100 A100 A100 A100 A100 test polyvinylchloride

From the results in Table 6, it is understood that in a curablecomposition using the polymer (B) of the present invention, it iseffective for an improvement in the adhesiveness thereof to increase theproportion of the amount of an aminosilane.

Example 15 and Comparative Example 13

Into 100 parts by weight of a reactive-silicon-group-containing polymershown in Table 7 (in each of these examples) were incorporated 55 partsby weight of DIDP, 120 parts by weight of the carbonate CCR, 20 parts byweight of the product TIPAQUE 8820, 2 parts by weight of the waxDISPARLON 6500, 1 part by weight of the product TINUVIN 327, and 1 partby weight of the product SANOL LS770. A three-paint-roll machine wasused to disperse these components into an even state. Thereafter,thereto were added 2 parts by weight of the product A-171, 3 parts byweight of that KBM 603, and 2 parts by weight of that NEOSTANN U-220H,and all the components were sufficiently mixed with each other. Anautorotation/orbital-revolution mixer was then used to mix thecomponents with each other into an even state, and defoam the mixture.In the same way as in Example 1, a sheet-form cured product having athickness of about 3 mm was produced therefrom. Thereafter, this sheetwas set into a sunshine carbon arc lamp type accelerating weatherresistance test machine (model number: S80, manufactured by Suga TestInstrument Co., Ltd.), which is an accelerating weather resistance testmachine. A weather resistance test was made under conditions that thetemperature of its black panel was 63° C., the temperature was 50° C.and the water-spraying period per 120 minutes was 18 minutes. Using sucha criterion that the quantity (Q value) and the size (S value) of cracksare each expressed in a numerical form, which is prescribed in the ISOstandard, the value of the product of the Q value and the S value wasdefined as the QS value, which is a scale representing the deteriorationdegree of the surface. The surface state of the sheet was quantitativelyrepresented after each of periods of 600 hours and 1300 hours. Theresults are shown in Table 7. A case where the QS value was 0 isrepresented by A; a case where the value was 10 or less, by B; and acase where the value was 20 or less, by C.

TABLE 7 Comparative Example 15 Example 13 Polymer B-1 S-1 Accelerated 600 h A B weather resistance 1300 h A C

From a comparison of Example 15 with Comparative Example 13, it isunderstood that the polymer (B-1) of the present invention is lower inQS value to be better in weather resistance than the polymer (S-1).

INDUSTRIAL APPLICABILITY

The polymer and the composition (of any one of the aspects) of thepresent invention are each suitable for being used as a curablecomposition or an adhesive composition, and are each usable for asticker, a sealing material for buildings, ships, automobiles, roads orothers, an adhesive, a waterproof material, a painted film waterproofmaterial, a mold making agent, a vibration proof material, a dampingmaterial, a soundproof material, a foaming material, a paint, a sprayingmaterial, and others. A cured product obtained by curing the curablecomposition of the present invention is excellent in softness andadhesiveness, and thus the product is more preferably used as a sealingmaterial or adhesive out of the above-mentioned articles.

The polymer or the composition of the present inventions is usable forvarious articles, such as electrical/electronic part materials such as asolar battery rear-surface sealing material, electrical/electronic partssuch as an insulating coat material for electric wires/cables,electrically insulating materials for devices, acoustic insulatingmaterials, elastic adhesives, binders, contact-type adhesives,spraying-type sealing materials, crack repairing materials, adhesivesfor tiling, adhesives for asphalt waterproof materials, powder paints,casting materials, rubbery materials for medical care, stickers formedical care, adhesive sheets for medical care, medical machine sealingmaterials, dental impression materials, food wrapping materials, sealingmaterials for joints between exterior members such as sizing boards,coating materials, slip-preventing coating materials, buffer materials,primers, electromagnetic wave shielding electroconductive materials,thermoconductive materials, hot melt materials, electrical/electronicpotting agents, films, gaskets, concrete reinforcing materials,adhesives for pre-adhesion, various molding materials, antirust andwaterproof sealing materials for end surfaces (cut regions) of awire-reinforced glass piece or laminated glass piece, and liquid sealingagents used for automobile parts, parts of large vehicles such as trucksand buses, train vehicle parts, aircraft parts, ship parts, electricalmachinery parts, and various mechanical parts, and others. Whenautomobiles are given as an example, the polymer or the composition isusable for various purposes, such as the attachment of plastic covers,trims, flanges, bumpers or windows, and the bonding and attachment ofinterior parts or exterior parts. The polymer or the composition is alsousable as various sealing compositions and bonding compositions sincethe polymer or the composition can be caused, by itself or by aid of aprimer, to adhere closely to various substrates, such as glass-,ceramic-material-, wood-, metal-, and resin-shaped products. The polymeror the curable composition of the present invention is usable forinterior panel adhesives, exterior panel adhesives, tiling adhesives,stone-material-laying adhesives, ceiling-finishing adhesives,floor-finishing adhesives, wall-finishing adhesives,vehicle-panel-usable adhesives,electrical/electronic/precision-instrument fabricating adhesives,adhesives for bonding a leather, a fiber product, a cloth, a paperpiece, a plate and a rubber, reactive and post-crosslinkablepressure-sensitive adhesives, direct-grazing sealing materials,laminated-glass-usable sealing materials, sealing materials for an SSGconstruction method, sealing materials for working joints for buildings,and materials for civil engineering or bridges. Furthermore, the polymeror the composition is usable as adhesive members, such as an adhesivetape and adhesive sheet.

1. A polymer (A) having, at one terminal moiety thereof, a terminalstructure having two or more carbon-carbon unsaturated bonds.
 2. Thepolymer (A) according to claim 1, wherein the terminal moiety has astructure represented by the following general formula (1):

wherein R¹ and R³ are each independently a bivalent bonding group having1 to 6 carbon atoms and an atom of the bonding group that is bonded toany carbon atom adjacent to the bonding group is any one of carbon,oxygen and nitrogen; R² and R⁴ are each independently hydrogen, or ahydrocarbon group having 1 to 10 carbon atoms; and n is an integer of 1to
 10. 3. The polymer (A) according to claim 1, wherein a hydroxyl groupor hydroxyl groups contained are 0.3 or less in number on average permolecule of the polymer (A).
 4. The polymer (A) according to claim 1,having a main skeleton which is a polyoxyalkylene polymer.
 5. A methodfor manufacturing the polymer (A) recited in claim 1, comprising:causing an alkali metal salt to act onto a polymer having, at a terminalthereof, a hydroxyl group in an amount of 0.6 equivalent or morerelative to the hydroxyl group amount in the polymer; causing theresultant to react with an epoxy compound having a carbon-carbonunsaturated bond; and further causing the resultant to react with ahalogenated hydrocarbon compound having a carbon-carbon unsaturatedbond.
 6. The method for manufacturing the polymer (A) according to claim5, wherein the alkali metal salt is a sodium alkoxide, the epoxycompound, which has a carbon-carbon unsaturated bond, is allyl glycidylether or methallyl glycidyl ether, and the halogenated hydrocarboncompound, which has a carbon-carbon unsaturated bond, is allyl chlorideor methallyl chloride.
 7. A reactive-silicon-group-containing polymer(B) having, at one terminal moiety thereof, a terminal structure havingtwo or more reactive silicon groups.
 8. Areactive-silicon-group-containing polymer (B), having reactive silicongroups which are 1.1 or more in number on average per terminal of thepolymer.
 9. A reactive-silicon-group-containing polymer (B), obtained byintroducing one or more reactive silicon groups into unsaturated bondsof the polymer (A) according to claim 1 by hydrosilylation reaction. 10.A method for manufacturing a reactive-silicon-group-containing polymer(B), comprising: introducing one or more reactive silicon groups intounsaturated bonds of the polymer (A) according to claim 1 byhydrosilylation reaction.
 11. A curing composition, comprising thepolymer (A) recited in claim
 1. 12. A composition, comprising thepolymer (B) recited in claim
 7. 13. The curable composition according toclaim 12, comprising, as the polymer (B), areactive-silicon-group-containing polymer (B1) in which a main chainskeleton is a polyoxyalkylene polymer, and further comprising a(meth)acrylate polymer (C) having one or more reactive silicon groups.14. The curable composition according to claim 13, wherein the reactivesilicon group(s) of the polymer (C) is/are (each) a reactive silicongroup (b3) represented by the following general formula (4):—SiR⁵ _(3-a)Y_(a)  (4) wherein R⁵(s) is/are (each independently) asubstituted or unsubstituted hydrocarbon group having 1 to 20 carbonatoms, Y is/are (each) a hydroxyl group or a hydrolyzable group, and ais any one of 1, 2 and 3 provided that a is 3 herein.
 15. The curablecomposition according to claim 13, comprising, as the polymer (B1), apolyoxyalkylene polymer having both species of one or more reactivesilicon groups (b2) which is/are (each) represented by the generalformula (4) in which a is 2, and one or more reactive silicon groups(b3) which is/are (each) represented by the general formula (4) in whicha is 3; and/or a polyoxyalkylene polymer having the reactive silicongroup(s) (b2) and a polyoxyalkylene polymer having the reactive silicongroup(s) (b3).
 16. The curable composition according to claim 15,wherein the reactive silicon group(s) (b2) is/are (each) amethyldimethoxysilyl group, and the reactive silicon group(s) (b3)is/are (each) a trimethoxysilyl group.
 17. The curable compositionaccording to claim 14, wherein the polymer (C) has trimethoxysilylgroups which are 1.27 or more in number on average per molecule of thepolymer (C).
 18. The curable composition according to claim 12, furthercomprising a polymer (D) having a reactive silicon group or reactivesilicon groups which are 0.5 or more and less than 1.2 in number onaverage per molecule of the polymer (D).
 19. The curable compositionaccording to claim 18, wherein the polymer (B) has a number-averagemolecular weight of 10000 or more and less than 35000, and the polymer(D) has a number-average molecular weight of 3000 or more and less than10000.
 20. The curable composition according to claim 12, furthercomprising an organopolysiloxane polymer (F) having a reactive silicongroup.